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Tuning structures and emissive properties in a

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Cite this: DOI: 10.1039/c7ce01988b

series of ZnIJII) and CdIJII) coordination polymers
containing dicarboxylic acids and nicotinamide
pillars†
Diana Chisca, ab Lilia Croitor, a Oleg Petuhov, c
Olga V. Kulikova, a

Galina F. Volodina, a Eduard B. Coropceanu, bc

Artëm E. Masunov *defg and Marina S. Fonari *a

Received 15th November 2017,
Accepted 12th December 2017
DOI: 10.1039/c7ce01988b
rsc.li/crystengcomm
New coordination polymers are reported. All polymers were prepared from a blend of four dicarboxylic
acids, three neutral nicotinamide ligands, and ZnIJII) or CdIJII) salts. The acids included: malonic (H2mal),
succinic (H2suc), adipic (H2adi), and 1,4-benzenedicarboxylic (H2bdc) acids, with all of them varying in
length and rigidity of the carbon skeletons. The neutral ligands included two positional isomers, iso-
nicotinamide (iso-nia) and nicotinamide (nia), and a nia thio-analogue, thionicotinamide (S-nia). The prepa-
ration resulted in eight CdIJII) and four ZnIJII) coordination polymers: [Cd2IJsuc)IJsucH)2IJnia)4]n (1),
{[CdIJsuc)IJnia)3]·H2O·dmf}n (2), {[CdIJadi)IJiso-nia)2]·dmf}n (3), [CdIJadi)IJiso-nia)2]n, (4), {[ZnIJmal)IJiso-nia)IJH2O)]
·dmf}n (5), {[CdIJmal)IJiso-nia)IJH2O)]·dmf}n (6), {[ZnIJmal)IJnia)IJH2O)]·dmf}n (7), {[CdIJmal)IJnia)IJH2O)]·dmf}n (8),
{[ZnIJmal)IJS-nia)IJH2O)]·dmf}n (9), {[ZnIJbdc)IJnia)2]·dmf}n (10), {[CdIJbdc)IJnia)2]·dmf}n (11), and nicotinamide-free
{[CdIJbdc)IJH2O)2IJdmf)]·dmf}n (12). Compounds 1–4 and 12 consist of one-dimensional arrays, while com-
pounds 5–11 are two-dimensional coordination arrays. The coordination cores in 1, 3, 4, 10, and 11 present
{M2IJCOO)2} (M = Zn, Cd) binuclear clusters, while the networks of 2, 5–9 and 12 are built on mononuclear
metal nodes with nicotinamide ligands acting as double or single pillars. The structure-confirmed single
crystal to single crystal transformation of 3 into 4 was detected and reported. While 1 and 4 are solvent-
free apohosts, the remaining solids acted as hosts of water and dmf solvent which are accommodated in
the crystal lattices as coordinated ligands or lattice solvents. The new solids were characterized by IR
spectroscopy, thermogravimetric analysis, and single-crystal and powder X-ray diffraction methods. The lu-
minescence properties of six as-synthesized coordination polymers and of some activated products are
reported. The influence of the metal, ligand, and solvent on tuning the structures and emission properties
was monitored, and the most impressive effects were interpreted with the help of TD-DFT computations.

a
Institute of Applied Physics, Academy of Sciences of R. Moldova, Academy str., 5
Introduction
MD2028, Chisinau, Moldova. E-mail: fonari.xray@phys.asm.md
b
Over the past decade we have witnessed growing interest in
Tiraspol State University, Iablocikin str. 5 MD2069, Chisinau, Moldova
c
Institute of Chemistry, Academy of Sciences of R. Moldova, Academy str., 3
the photochemistry of luminescent ZnIJII) and CdIJII) coordina-
MD2028, Chisinau, Moldova tion polymers (CPs) including metal organic frameworks
d
NanoScience Technology Center, Department of Chemistry, Department of (MOFs),1 crystalline solids that successfully combine remark-
Physics, and, Florida Solar Energy Center, University of Central Florida, 12424 able optical properties and porosity in the form of numerous
Research Parkway, Ste. 400, Orlando, Florida 32826, USA.
reported multifunctional materials.2–5 Colorless d10 metal
E-mail: amasunov@ucf.edu
e
South Ural State University, Lenin pr. 76, Chelyabinsk 454080, Russia
ions, ZnIJII) and CdIJII), can adopt different coordination geom-
f
Photochemistry Center RAS, ul. Novatorov 7a, Moscow 119421, Russia etries suitable for the construction of luminescent coordina-
g
National Research Nuclear University MEPhI (Moscow Engineering Physics tion complexes. Two transition types of electronic excited
Institute), Kashirskoye shosse 31, Moscow, 115409, Russia states, ligand-to-ligand change-transfer (LLCT) and ligand-to-
† Electronic supplementary information (ESI) available: Synthetic procedures,
metal change-transfer (LMCT), were reported in these com-
selected bond distances and angles, hydrogen bonds, thermogravimetric data
and plots of IR spectra and XRPD patterns for some activated products.
plexes.6 This fact is a consequence of the d10 electronic con-
1578395–1578406. For ESI and crystallographic data in CIF or other electronic figuration of these ions, with flexible coordination allowing a
format see DOI: 10.1039/c7ce01988b wide variety of geometries. Moreover, the closed-shell metal

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Paper
ion configuration explains the absence of excitation
quenching due to d–d transitions. This allows for the efficient
emission of these hybrid materials, making them useful as
chemical sensors,7 including in the detection of hazardous
small molecules, like explosives,8–14 volatile organic com-
pounds (VOCs),15–17 and charged species.18 In addition, these
materials may be used for sensing excimer formation7 and
other processes leading to emission quenching/enhancement.
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The protocols for tuning the photophysical behavior of
metal–organic materials by utilizing suitable molecular self-
assembly of luminophores and photochromic components
were reported. This tuning may be accomplished by varying
the temperature, templates, ligands and pH of the reaction
medium.19–22 Numerous applications rely on either the linear
optical properties of Zn and Cd coordination networks or
their non-linear optical properties such as second harmonic
generation (SHG),23–26 two-photon absorption (2PA)27,28 and
third harmonic generation (THG).29,30 Other applications use
emissive coordination networks as co-sensitizers in dye-
synthetized solar cells (DSSCs),31 for energy conversion and
light harvesting. All of them rely on well-defined crystal struc-
tures and controllable chromophore distances.32 This wide
range of applications motivates crystal engineers to extend CP
and MOF libraries in their effort to attain new materials with
higher performance. Non-centrosymmetric space groups,
which are a prerequisite for efficient SHG in the solid state
can be obtained for CPs and MOFs using a crystal engineer-
ing approach of rational design. In the absence of chiral li-
gands, the asymmetry necessary for SHG is achieved either
via asymmetric metal coordination cores (tetrahedral for Zn
or pentagonal bipyramidal for Cd), or via conformational flex-
ibility of symmetric ligands.33–35 Another strategy employs li-
gands with an asymmetric push–pull geometry (donor–π-
chromophore–acceptor = D–π–A), such as pyridine-n-oximes,
nicotinic acid and nicotinamide derivatives.25,36–39 Several ex-
amples were reported, where the same ligand can provide
multiple optical properties (luminescence and SHG, lumines-
cence and 2PA, luminescence and DSSCs),31,33,40 underlining
the benefits of this strategy.
Flexible porous CPs along with rigid MOFs41 may also
serve as smart materials, responsive to external stimuli. They
allow tuning of their sensing properties, such as color, ad-
sorption/desorption rate, solvent/gas uptake/release, emission
range etc. Pillar-layered (PL) hybrid materials, combining two
different structural units, a layer and a pillar, demonstrated
major advances in the past few years.42–47 The structural flexi-
bility and response to different guests and external physical
stimuli render PL-MOFs good candidates for investigating
solid state structural transformations and reactions. Dicar-
boxylic acids with different chain lengths and conformational
flexibilities and transition metals with variable coordination
polyhedra were found to be useful building units for this
purpose.48–63 As a family of neutral nitrogen-donor co-li-
gands, amide-bridged polypyridine compounds with
structure-dependent properties have been introduced into
such metal carboxylate systems in the past decade.50,52–58,60,63
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The introduction of neutral nitrogen-donor co-ligands into
such metal carboxylate systems is an effective strategy for
tuning the architectures and functionalities of CPs. The re-
sponse to the external stimuli, thermal stability and mechani-
cal strength are determined by coordination bonds, as well as
hydrogen bonds between the pillars or between pillars and
the carboxylate framework. Our recent work with nicotin-
amide or oxime ligands used as pillars demonstrated the as-
sociation of coordination motifs into higher dimensional net-
works, 1D > 2D > 3D; 2D > 3D.36,37,64–66 Some of these
materials crystallizing in the non-centrosymmetric space
groups favorable for SHG showed their responsiveness to ex-
ternal stimuli upon solvent removal/uptake and stability even
under the conditions of solid state transformations.64–66
Herein, we focus on the possibility of reproducing the
structural motifs in order to extend this series of coordina-
tion polymers by varying the d10 metals, ZnIJII) or CdIJII), the
length and conformational flexibility of dicarboxylic acids,
and the nicotinamide pillar ligands (Scheme 1) in order to
study and tune the optical properties of the prepared
compounds.
This study is aimed at the evaluation of the optical proper-
ties of a new series of Zn and Cd coordination polymers and
their dependence on the ligands and guest inclusion. Eleven
single- and double-pillared 1D and 2D CPs, [Cd2IJsuc)IJsucH)2-
IJnia)4]n (1), {[CdIJsuc)IJnia)3]·H2O·dmf}n (2), {[CdIJadi)IJiso-nia)2]
·dmf}n (3), [CdIJadi)IJiso-nia)2]n (4), {[ZnIJmal)IJiso-nia)IJH2O)]
·dmf}n (5), {[CdIJmal)IJiso-nia)IJH2O)]·dmf}n (6), {[ZnIJmal)IJnia)-
IJH2O)]·dmf}n (7), {[CdIJmal)IJnia)IJH2O)]·dmf}n (8), {[ZnIJmal)IJS-
nia)IJH2O)]·dmf}n (9), {[ZnIJbdc)IJnia)2]·dmf}n (10), {[CdIJbdc)-
IJnia)2]·dmf}n (11), and nicotinamide-free {[CdIJbdc)IJH2O)2-
IJdmf)]·dmf}n (12) (where malonic acid = H2mal, succinic acid
= H2suc, adipic acid = H2adi, 1,4-benzenedicarboxylic acid =
H2bdc, isonicotinamide = iso-nia, nicotinamide = nia, and
thionicotinamide = S-nia), were obtained by solvent co-
crystallization (1, 2, 5–12) and single-crystal to single-crystal
transformation (3 into 4). The influence of the metal, ligand,
and solvent on tuning the emission properties was investi-
gated, and the most significant effects were interpreted with
the help of TD-DFT simulations.
Experimental and computational
details
Materials and methods
All reagents and solvents were obtained from commercial
sources and used without further purification. Elemental
analyses were performed on an Elementar Analysensysteme
GmbH Vario El III elemental analyzer. The IR spectra were
obtained with Nujol using a FT IR Spectrum-100 Perkin
Elmer spectrometer in the range of 400–4000 cm−1.
TGA experiments were carried out in a Derivatograph
Q-1500 thermal analyzer in an air flow at a heating rate of 10
°C min−1 in the temperature range of 25–1100 °C.
Luminescence experiments were performed using a pulsed
nitrogen laser (337.1 nm) at 300 °C. The excitation pulse
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Scheme 1 Schematic representation of the ligands used in this study with abbreviations.
duration is 15 ns, the repetition frequency is 50 Hz, and the
pulse energy is 0.2 mJ. Radiation was detected with the help
of a FEU-79 (multi-alkali photocathode, SbIJNa2K) with
adsorbed cesium layer on the surface, characteristics of S20
type). The intrinsic time of the recording system is 20 ns. The
duration of the afterglow (at 300 °C) for all substances stud-
ied was less than the temporal resolution of the recording
system.
X-ray powder diffraction data were collected with a DRON-
UM X-ray powder diffractometer equipped with an Fe-Kα ra-
diation (λ = 1.93604 Å, Mn filter) source. The data were col-
lected over an angle range of 5–50° at a scanning speed of 2°
per minute.
Single crystal diffraction measurements for 1–12 were
carried out on an Xcalibur E diffractometer equipped with
a CCD area detector and a graphite monochromator utiliz-
ing MoKα radiation at room temperature. The final unit
cell dimensions were obtained and refined on the entire
dataset. All calculations to solve the structures and to re-
fine the models proposed were carried out with the
SHELXS97 and SHELXL2014 program packages.67,68 Hydro-
gen atoms attached to carbon atoms were positioned geo-
metrically and treated as riding atoms using SHELXL de-
fault parameters with UisoIJH) = 1.2UeqIJC). The O(N)-bound
H-atoms were determined from differential Fourier maps at
the intermediate stages of the refinement and their posi-
tions were restrained using the DFIX instruction [OIJN)–H =
0.86 Å]. These hydrogen atoms were refined with the isotro-
pic displacement parameter UisoIJH) = 1.5UeqIJO,N). The sol-
vent (dmf) disorder was resolved in structures 5 and 12,
with the dmf molecules disordered over two positions with
the partial occupancies of 0.53IJ2) : 0.47IJ2) in 5 and 0.5 : 0.5
in 12. In the isomorphous structures of 7–9 the nicotin-
amide pillars nia and S-nia and dmf molecules are disor-
dered over two positions in a synchronized order with par-
tial occupancies of 0.539IJ12) : 0.461IJ12) in 7, 0.584IJ12) :
0.416IJ12) in 8, and 0.520IJ9) : 0.480IJ9) in 9. The X-ray data
and the details of the refinement for 1–12 are summarized
in Table 1, the selected geometric parameters are summa-
rized in Table S1,† and the H-bonding parameters are given
in Table S2.†
Crystallographic data of the new structures reported
herein were deposited with the Cambridge Crystallographic
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Data Centre and allocated the deposition numbers CCDC
1578395–1578406.
Computational methods
All calculations were performed at the density functional
theory (DFT) level using Gaussian 09.69 We employed SDD
Stuttgart effective core potentials for the metal atoms70 and
the D95 basis set for the other atoms,71 combined with the
M05-QX exchange-correlation functional (formerly known as
M05-1¼X).72 This functional was obtained by interpolation be-
tween M05 and M05-2X functionals73 and includes 35% of
the exact exchange. Emission wavelengths were calculated
using the optimized geometry of the lowest excited state
with substantial oscillator strength. Prediction of the linear
absorption spectra using linear response time dependent
DFT74 (TD-DFT) nowadays becomes a routine.75,76 Optimiza-
tion on the excited state potential surface allowed us to suc-
cessfully predict vertical emission77,78 (including dual emis-
sion43,79,80) and photochemical reaction81–85 processes.
Orbital plots were prepared using the Molden visualization
program.86
Results and discussion
Synthesis and IR characterization
Two groups of studied compounds include five (1–4, 12) 1D
and seven (5–11) 2D CPs. All compounds were obtained by
conventional solvent cocrystallization, with the best ratios of
starting compounds found empirically to achieve better yield
and reproducible products in each case. To exclude the pos-
sible intervention of starting carboxylates (such as acetate)
the syntheses were carried out with CdIJBF4)2 and ZnIJBF4)2
salts as starting materials with easy-leaving tetrafluoroborate
anions. All compounds were prepared similarly by mixing
CdIJBF4)2·6H2O or ZnIJBF4)2·6H2O, dicarboxylic acids and nico-
tinamide ligands in a 1 : 1 : 2 ratio in a mixture of CH3OH :
dmf : H2O or CH3OH : dmf upon heating and crystals were
precipitated upon cooling until room temperature. The de-
tails of the synthetic procedures are given in the ESI.† The
IR spectra of 1–11 reveal similarities with slight displace-
ment of vibration signals. In all spectra the asymmetric
stretching vibrations of carboxylic groups (νasCOO) are ob-
served at 1550 cm−1 in 1, 1534 cm−1 in 2, 1581, 1554 cm−1
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Table 1 Crystal data and structure refinement parameters of 1–12

1 2 3 4 5 6
Empirical formula C18H19CdN4O8 C25H31CdN7O9 C21H27CdN5O7 C18H20CdN4O6 C12H17N3O7Zn C12H17CdN3O7
Fw (g mol−1) 531.77 685.97 573.87 500.78 380.65 427.68
Crystal system Monoclinic Monoclinic Triclinic Triclinic Monoclinic Monoclinic
Space group P21/n P21/c P1̄ P1̄ P21/n P21/n
a/Å 11.4313(3) 14.4827(3) 9.1569(3) 9.240(2) 7.1206(2) 7.2332(3)
b/Å 14.6649(3) 10.7160(2) 9.3193(5) 9.716(3) 30.8546IJ13) 29.3496IJ10)
c/Å 12.9413(4) 18.3369(4) 14.7832(7) 11.092(5) 7.4367(2) 7.6871(3)
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α/deg 90 90 74.014(5) 100.29(3) 90 90

β/deg 102.751(3) 98.4010IJ19) 81.153(4) 90.03(2) 90.534(3) 94.263(3)
γ/deg 90 90 79.432(4) 100.76(2) 90 90
V/Å3 2115.96IJ10) 2815.28IJ10) 1185.04IJ10) 961.9(5) 1633.78IJ10) 1627.38IJ10)
Z 4 4 2 2 4 4
Dcalcd Mg m−3 1.669 1.618 1.608 1.729 1.548 1.746
μ/mm−1 1.085 0.841 0.973 1.179 1.541 1.380
FIJ000) 1068 1400 584 504 784 856
Reflns collected/unique 6695/3697 11 268/5193 7276/4615 5888/3532 12 190/3037 5522/3021
[RIJint) = 0.0334] [RIJint) = 0.0380] [RIJint) = 0.0360] [RIJint) = 0.1038] [RIJint) = 0.0366] [RIJint) = 0.0243]
Data/restraints/parameters 3697/6/295 5193/12/403 4615/6/321 3532/90/262 3037/140/266 3021/6/220
GOF on F 2 1.005 0.998 0.999 1.013 1.088 1.062
R indices [I > 2σ(I)], 0.0411, 0.0760 0.0389, 0.0648 0.0466, 0.0610 0.1235, 0.2738 0.0587, 0.1584 0.0337, 0.0642
R1, wR2
R indices (all data) R1, wR2 0.0630, 0.0844 0.0588, 0.0715 0.0677, 0.0685 0.2304, 0.3390 0.0640, 0.1609 0.0447, 0.0691

7 8 9 10 11 12
Empirical formula C12H17N3O7Zn C12H17CdN3O7 C12H17N3O6SZn C23H23N5O7Zn C23H23CdN5O7 C14H22CdN2O8
Fw (g mol−1) 380.65 427.68 396.71 546.83 593.86 458.73
Crystal system Orthorhombic Orthorhombic Orthorhombic Tetragonal Tetragonal Triclinic
Space group Pna21 Pna21 Pna21 I41cd I41cd P1̄
a/Å 30.7094IJ13) 31.0771IJ15) 31.782(2) 17.9994(3) 18.3535(7) 6.0843(4)
b/Å 7.0123(3) 7.1271(4) 7.0949(5) 17.9994(3) 18.3535(7) 13.0084(6)
c/Å 7.4215(4) 7.6076(4) 7.3953(5) 28.3709(7) 28.8470IJ13) 23.5288IJ12)
α/deg 90 90 90 90 90 97.915(4)
β/deg 90 90 90 90 90 95.390(5)
γ/deg 90 90 90 90 90 95.166(4)
V/Å3 1598.16IJ13) 1685.00IJ15) 1667.59IJ18) 9191.6(4) 9717.1(8) 1826.29IJ17)
Z 4 4 4 16 16 4
Dcalcd Mg m−3 1.582 1.686 1.580 1.581 1.624 1.668
μ/mm−1 1.576 1.333 1.630 1.125 0.952 1.238
FIJ000) 784 856 816 4512 4800 928
Reflns collected/unique 3621/2191 3679/2472 3607/2151 9515/3680 11 794/4078 9774/6405
[RIJint) = 0.0385] [RIJint) = 0.0383] [RIJint) = 0.0379] [RIJint) = 0.0270] [RIJint) = 0.0314] [RIJint) = 0.0213]
Data/restraints/parameters 2191/356/324 2472/368/324 2151/356/330 3680/7/339 4078/7/339 6405/18/520
GOF on F 2 1.019 0.994 1.022 1.054 1.020 0.979
R indices [I > 2σ(I)], 0.0468, 0.1106 0.0478, 0.0640 0.0454, 0.1010 0.0277, 0.0608 0.0328, 0.0799 0.0336, 0.0598
R1, wR2
R indices (all data) R1, wR2 0.0636, 0.1231 0.0829, 0.0724 0.0581, 0.1110 0.0331, 0.0634 0.0405, 0.0855 0.0492, 0.0663

in 3, 1571, 1552 cm−1 in 5, 1550, 1559 cm−1 in 6, 1566 cm−1
in 7, 1552 cm−1 in 8, 1555 cm−1 in 9, 1577 cm−1 in 10, 1578
cm−1 in 11, and 1560 and 1500 cm−1 in 12. The νsIJCOO−)
bands are observed at 1388 cm−1 (1), 1416 and 1388 cm−1
(2), 1416 cm−1 (3), 1392 and 1346 cm−1 (5), 1394 and 1342
cm−1 (6), 1388 and 1350 cm−1 (7), 1380 and 1342 cm−1 (8),
1357 and 1330 cm−1 (9), 1392 cm−1 (10), 1384 cm−1 (11), and
1382 cm−1 (12). Differences Δν = νasIJCOO−) − νsIJCOO−) vary in
the range 118–225 cm−1 which corroborate the bidentate
and monodentate coordination of carboxylic groups. The ab-
sorption bands at ∼3321–3737 cm−1 can be attributed to the
O–H groups. Characteristic vibration bands at ∼3138–3229
cm−1 belong to NH2 group stretching vibration of the nico-
tinamide ligand. In all spectra, the C–H deformation modes
are present at ∼687–978 cm−1. The IR spectrum for com-
pound 12 differs from all others because the system lacks
the nicotinamide ligand and thus its characteristic bands.
Crystal study
One-dimensional coordination polymers. Using succinic
acid as a linker and nicotinamide as a pillar (Scheme 1) two
new 1D coordination polymers, 1 and 2, were obtained. In
compound 1, [Cd2IJsuc)IJHsuc)2IJnia)4]n, that crystallizes in the
monoclinic P21/n space group, the centrosymmetric binuclear
cluster {Cd2IJCOO)2} (Fig. 1a) acts as a secondary building unit
(SBU) in the 1D coordination array. The succinate anions are
present in mono- and di-deprotonated states, Hsuc− and

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Fig. 1 (a) View of the {Cd2IJCCOO)2} binuclear unit in 1 with a partial atom numbering scheme; (b) and (c) association of the coordination arrays
into H-bonded layers via the centrosymmetric R22(8) carboxylic and R22(8) amide homosynthons. C-Bound H-atoms are omitted for clarity.
suc2−. In the binuclear SBU each CdIJII) atom adopts a slightly
distorted octahedral geometry with the N2O4-set of donor
atoms (Table S1†) going from two Hsuc− and one suc2− resi-
dues in the equatorial plane, and two nia ligands in the axial
terminal positions. The Hsuc− anion, as a bidentate bridging
ligand, mediates two Cd atoms in a syn–syn mode, with the
Cd⋯Cd separation across the triatomic bridge being
3.9114(6) Å. In contrast, the suc2− anion acts as a double
bridge with a bis-chelating mode, with the Cd⋯Cd separa-
tion across it being 9.1244(6) Å. Two terminal nia pillars are
oriented nearly perpendicular to the coordination plane, and
their pyridine rings twist at an angle of 17.04°. Between the
coordination arrays, there are two types of centrosymmetric
R22(8) homomeric supramolecular synthons, the amide ones,
based on the two NH⋯OIJOC) hydrogen bonds (N⋯O dis-
tances = 2.881(5) and 2.964(5) Å, Table S2†), and the carbox-
ylic one, based on the two COOH⋯OIJOC) hydrogen bonds,
(O⋯O distance = 2.618 Å, Table S2†), each leading to the ag-
gregation of the coordination chains into 2D H-bonded
sheets (Fig. 1b and c) whose two-fold interpenetration affords
a dense solvent-free 3D H-bonded network. The use of cad-
mium tetrafluoroborate as a starting salt with an easy leaving
BF4− anion allowed a more homogeneous structure that con-
tains only one type of coordination array to be obtained, con-
trary to the reported CoIJII) compound {[Co2IJsuc)IJCH3COO)2-
IJiso-nia)4]ijCo2IJsuc)IJsucH)2IJiso-nia)4]·2dmf}n that consists of
two types of coordination arrays.66
Compound 2 with the composition {[CdIJsuc)IJnia)3]·(H2O
·dmf)}n was obtained from a more concentrated solution with
a different ratio of CH3OH : dmf solvent with the CdIJII) cation
as a single node. The CdIJII) coordination geometry is de-
scribed as a pentagonal bipyramid in the N3O4 coordination
environment (Table S1†). Two suc2− anions coordinated in a
bidentate chelating mode and one monodentate nia-ligand
occupy the equatorial plane, while two other nia ligands oc-
cupy the axial vertexes (Fig. 2a). The suc2− anion, being in a
gauche-conformation with a –C–C– torsion angle of 66.54°
links two successive Cd atoms with a distance of 6.9118(4) Å,
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which is significantly shorter compared with the 9.1244(6) Å
in 1 where the centrosymmetric suc2− anion is present in an
extended ideal anti-conformation. The resulting helical coor-
dination array is extended parallel to the crystallographic b
axis with the perfectly overlapping nia ligands from the
neighboring metal centers (Fig. 2b). Of the three coordinated
nia ligands, one is found in the centrosymmetric R22(8)
amide-homosynthon (N⋯O = 3.029(4) Å) while the two others
through amido-groups are involved in the hydrogen bonding
with the solvents, dmf and water, leading to the solvents' up-
take in the crystal lattice.
Compound 3 with the composition {[CdIJadi)IJiso-nia)2]
·dmf}n is isomorphous to its CoIJII) analogue66 with a minor
increase in the unit cell volume (2.44%) and other linear geo-
metric parameters associated with a larger CdIJII) atomic ra-
dius (Table S1†). Similarly, solvent evacuation from 3 that
was accompanied by SC–SC transformation, resulted in the
solvent-free apohost 4 [CdIJadi)IJiso-nia)2]n (Fig. 3), which is
again isomorphous to its CoIJII) analogue.66
As listed in Table 1, both solids 3 and 4 crystallize in the
triclinic unit cell. Solvent evacuation resulted in small elonga-
tion of two unit cell parameters (a and b) and contraction of
the other one (c) accompanied by contraction of the total unit
cell volume by 223.14 Å3 or 23.2%, the value closely
approaching the calculated value for the solvent accessible
voids (SAVs) in 3 (216.01 Å3 or 18.2%). The single crystal
X-ray data indicated that the SC–SC transformation did not
affect the architecture of 1D coordination arrays. Both the
structures of 3 and 4 present 1D double coordination arrays
(Fig. 4a) built of alternating 8- and 20-membered meta-
llocycles through two carboxylic groups that act in a
bidentate bridging mode, and link centrosymmetric
binuclear {Cd2IJCOO)2} SBUs with Cd⋯Cd separations of
3.9722(4) Å in 3 and 4.095(2) in 4 and the next short separa-
tion between two Cd atoms being 6.7549(6) Å in 3 and
7.513(3) in 4 (Fig. 4b). The CdIJII) coordination cores are
distorted octahedra with the N2O4-sets of donor atoms com-
ing from three adi residues in the equatorial plane and two
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Fig. 2 (a) ORTEP drawing of the CdIJII) coordination core in 2 with a partial atom numbering scheme; (b) fragments of the two helical coordination
arrays in 2 combined via a H-bonded amide supramolecular synthon.
Fig. 3 (a) View of the crystals of 3; (b) view of the activated crystals of
3′ which is a mixture of 3 and 4 after heating in a vacuum.
iso-nia ligands in the terminal axial positions, oriented virtu-
ally perpendicular to the metal–carboxylate coordination
plane, and being situated in the nearly parallel planes as in-
dicated by the twisted angles of 7.64° in 3 and 2.69° in 4 be-
tween their pyridine rings. The single crystal X-ray study indi-
cates that the 1D host framework is retained during the
transformation, accompanied by rotation of the pillars, redis-
tribution of the hydrogen bonds, and slippage and reduced
separations between the neighboring coordination arrays
(Fig. 4c). The structure of the dried form of 4 has neither
dmf solvent nor voids for its inclusion. It should be men-
tioned that for CdIJII) compound 3 the process of solvent evac-
uation took a longer time and was significantly more difficult
to proceed than for the isomorphous CoIJII) compound.66 The
increased duration of this procedure resulted in significant
deterioration of the crystal quality, hampering the search for
crystals of the solvent-free apohost 4 in the bulk.
Two-dimensional coordination polymers. For the ZnIJII)/
CdIJII)–malonic acid–nicotinamide ligand system (Scheme 1)
by tuning the type of metal and nicotinamide ligand while
keeping the acid the same, five layered CPs 5–9 with the gen-
eral formula {[MIJmal)IJB)IJH2O)]·dmf}n, where M = Zn, B = iso-
nia, nia, S-nia for 5, 7, 9; and M = Cd, B = iso-nia, nia for 6
and 8 were obtained. The topology and architecture of 2D co-
ordination networks are fully identical in all of them and
agree with some reported structures.36,87–90 Compounds 5–9
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fall into two isomorphous series: 5, 6 and 7–9
(Table 1); compounds from the second group are also isomor-
phous with the Co(II) analogue.66 In each compound, the sin-
gle metal in a distorted octahedral NO5-geometry (Table S1†)
represents the building block made up of two-dimensional ar-
rangements of metal atoms linked by malonate groups in an
anti–syn bridging mode. The metal atom in each compound,
5–9, is coordinated with four carboxylate-oxygens in the equa-
torial plane and a nitrogen atom and a water molecule in the
axial positions (Fig. 5a). The replacement of the metal and the
base does not affect the architecture of the coordination layer
(Fig. 5b). These results demonstrate the stability and repro-
ducibility of a metal–malonate 2D coordination network that
is reported as a unique 2D grid in the case of a monodentate
N-base or as part of a 3D coordination polymer in the case of
a bidentate N-ligand.36,87–90 The geometry of the pillar has an
impact on the rigidity of the supramolecular network and on
the crystal packing. The inconsistencies appear at the levels of
the packing of acentric coordination layers and of the struc-
tures' disordering: no disordering of the coordination net-
work has been found in 5 and 6 where the iso-nia pillars are
oriented strictly perpendicular to the coordination layer,
connected through the centrosymmetric amide homosynthon
(Fig. 5c). The centrosymmetric crystal packing in 5 and 6 (P21/
n space group) that arises from the generation of a centrosym-
metric R22(8) homosynthon between the coordination layers is
governed by the linear geometry of the iso-nia molecule which
leads to the aggregation of the 2D coordination layers into a
3D H-bonded network. This is a principal distinction from
the noncentrosymmetric crystal packing in 7–9 (Pna21 space
group) with unfavorable meta-arrangement of the
amidoIJthioamido)-groups in nia and S-nia molecules that, in-
stead of rigid amido synthon in 5 and 6, provide only a single
NH⋯OIJS) hydrogen bond in 7–9, that results in the synchro-
nization of the disordering of pillars and accommodated dmf
molecules (Fig. S1d†). Now we see that the flexible behavior of
the networks of 7–9 most probably is dictated by the geometry
of nia and S-nia ligands unfavorable for tight H-bonding con-
trary to the iso-nia ligand that provides a robust
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Fig. 4 (a) View of the coordination array in 3. (b) ORTEP drawing of the {Cd2IJCOO)2} binuclear unit in 3 which is identical to 4. (c) Mode of
association of the coordination arrays in 3 via NHIJamide)⋯OIJamide) hydrogen bonds; (d) mode of association of the coordination arrays in 4 via
NHIJamide)⋯OIJcarboxylate) hydrogen bonds accompanied by slippage of the coordination arrays and contraction of the crystallographic c axis. In
all images, the C-bound H-atoms are omitted for clarity.

Fig. 5 (a) Coordination environment of CdIJII) in 5 which is identical to those in 6–9. (b) Fragment of a coordination layer in 5 identical to those in
6–9. (c). Association of coordination layers into a 3D network via an R22(8) centrosymmetric amide homosynthon, NHIJNH2)⋯OIJCO), in 5.
C-Bound H-atoms and dmf solvent molecules are omitted for clarity.

centrosymmetric supramolecular amide synthon between the
coordination layers (Fig. 5c, Table S2†).
The combination of ZnIJII)/CdIJII) salts with H2bdc acid and
the nia ligand resulted in two isomorphous compounds 10
and 11 with the composition {[MIJbdc)IJnia)2]·dmf}n, (M = Zn,
Cd). In the case of iso-nia the unreported 1D Cd-
terephthalate 12 was obtained. Both 10 and 11 crystallize in
the non-centrosymmetric I41cd space group, where the
{M2IJCOO)2} binuclear units reside on two-fold axes and ex-
hibit a two-fold symmetry. Each metal atom adjusts the N2O4-
distorted octahedral geometry, consisting of four oxygen
atoms from three bdc ligands in the equatorial plane (Fig. 6a,
Table S1†). The bdc linker shows two bridging modes,
namely syn,syn-bidentate-bridging within the cluster and bis-
monodentate between the clusters. The metal⋯metal separa-
tions across the two triatomic bridges are 4.0660(5) Å for Zn
and 4.0076(7) Å for Cd, and those across the bdc ligand are
10.8324(5) and 10.9422(5) Å for Zn and 11.0985(7) and
11.2154(8) for Cd. The bdc residues are oriented in the layer's
mean plane while the two nia ligands are oriented perpendic-
ular to the same plane. They are situated approximately in
parallel planes as indicated by the twisted angles of 8.28° for

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Fig. 6 (a) View of the {Cd2IJCCOO)2} binuclear unit in 11 with a partial atom numbering scheme; (b) fragment of the coordination layer with a (4,4)
sql topology. C-Bound H atoms are omitted for clarity.
Zn and 6.30° for Cd between the pyridine rings of two nia
molecules. The 2D coordination networks with a (4,4) sql to-
pology have square meshes with dimensions of 12.73 × 12.73
Å2 in 10 and 12.98 × 12.98 Å2 in 11 calculated as the separa-
tions between the centroids of the binuclear units (Fig. 6b).
The crystal packing is reinforced via NH⋯OIJCOO−) hydrogen
bonds with participation from all NH2-donors (Table S2†)
which combine the staggered layers into a 3D network, cap-
turing the dmf in the rectangular cages. The tight dmf ac-
commodation in the crystal lattices is enforced exclusively by
stacking interactions between the π-electronic systems of dmf
and bdc entities oriented in parallel modes since all hydro-
gen bonds are realized within the host network. The crystal
structures of 10 and 11 show no differences from those of
their CoIJII) analogue,66 and their 2D architecture is also iden-
tical to that of {[MIJbdc)IJ4-pyao)2]·dmf}n with M = Zn, Cd and
pyridine-4-aldoxime (4-pyao) as a pillar.64
In the {Cd-bdc} 1D coordination polymer with the simpli-
fied formula {[CdIJbdc)IJH2O)2IJdmf)]·dmf}n (12) the asymmetric
unit comprises two crystallographically unique metal atoms,
Cd(1) and Cd(2), four coordinated water molecules, two coor-
dinated dmf molecules, and one and two halves of bdc li-
gands, the latter ones residing on inversion centers (Fig. 7a).
The lattice solvents are two dmf molecules, one being or-
dered and the other disordered around an inversion center.
Both Cd atoms have identical heptacoordinated O7 coordina-
tion cores with a pentagonal bipyramidal geometry (Table
S1†), five oxygen atoms in the equatorial planes going from
two bidentate bridging bdc residues and one water molecule,
a water molecule again occupying the axial positions and the
dmf solvent arranged perpendicular to the coordination
plane. The association of the 1D arrays into a 2D H-bonded
layer roughly parallel to the plane (0 1 −3) occurs via equato-
rial water molecules O(1w) and O(4w) by means of four
OHIJw)⋯OIJCOO−) hydrogen bonds (O⋯O = 2.741(3), 2.778(4),
2.781(4), 3.009(3) Å) The shortest Cd⋯Cd separation within
this H-bonded layer across water molecules is 6.084 Å (identi-
cal for both Cd1⋯Cd1 and Cd2⋯Cd2 separation) (Fig. 7b).
In the [−1 1 −1] direction the coordination arrays combine
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into a H-bonded layer again via OHIJw)⋯OIJw) hydrogen
bonds with the shortest Cd1⋯Cd2 separation of 6.376 Å. The
association of these two 2D H-bonded motifs provides 3D H-
bonded network with the cages being occupied by the two
crystallographically different dmf solvent molecules. One of
them acts as the pillar being coordinated to the Cd atoms
through the carbonyl oxygen atom, while the second one acts
as the lattice solvent being situated parallel to the bdc array
and held in the crystal lattice via OH⋯O(OC) hydrogen
bonds with coordinated water molecules (Fig. 7c).
Evacuation of guest molecules from coordination networks
supported by TGA, IR and XRPD studies
The important factor in seeking and developing new metal–or-
ganic porous materials is their stability upon guest removal
that allows tracing the difference in the emission of the
solvent-loaded and solvent-free (activated) networks. Except
for the solvent-free apohosts 1 and 4, all other solids reported
herein contain cavities filled with water and/or dmf guest mol-
ecules. Moreover, in 5–9 water molecules occupy one of the ax-
ial positions in the metal's coordination cores, while in 12
both water and dmf act both as coordinated ligands and as lat-
tice solvents. The lattice solvents are held in the pores via hy-
drogen bonds with the coordination network, while in 10 and
11 they are held via stacking interactions with the π-system of
the bdc ligand. The cumulative solvent content varies from
12.29 wt% in 11 till 39.67 wt% in 12. The solvent accessible
voids (SAVs) adopt the shapes of open channels in 2 (555 Å3)
and in 5–9, discrete cages in 10 and 11 (1332 Å3; 1663 Å3), and
infinite surfaces in 3 (216 Å3) and 12 (1089 Å3) (Fig. S1†).
A combined TGA and XRPD technique was used to prove
the frameworks' performance and exclusion of the guest mol-
ecules from the crystalline solids. Since our recent studies on
CoIJII) networks66 indicated a strong confinement effect of
dmf in the crystal {[CoIJbdc)IJnia)2]·dmf}n due to adsorbate–ad-
sorbent interactions and an impossibility to evolve the sol-
vent without the destruction of coordination networks, the
isomorphous Zn and Cd compounds 10 and 11 were not
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Fig. 7 (a) Fragment of the coordination array in 12 with a partial labeling scheme. (b) Association of the 1D coordination arrays into a H-bonded
layer via OHIJw)⋯OIJCOO) hydrogen bonds. (c) Mode of dmf accommodation in the crystal lattice in 12.
tested as candidates for the SC–SC transformation in this
work. Therefore, six samples 3, 5, 6, 7, 9 and 12 with open
voids were studied. For all of them, the thermal degradation
pathways are in line with their crystal structures and occur as
multistep processes that include the consecutive loss of sol-
vents followed by the decomposition of the coordination
backbones. The loss of solvents was observed as a well-
resolved process completed at 225 °C in 3, 196 °C in 5–7 and
9 and 259 °C in 12. The subsequent degradation of the
hetero-ligand coordination grids occurs as a two-step process
in 3, 5–7 and 9, while the carboxylate backbone in 12 decom-
poses in one step (Fig. 8, Fig. S2, Table S3†).
Based on the TGA data, we attempted to perform solvent
evacuation in a vacuum, and freshly ground samples of 3, 5,
7, and 12 were subjected to activation in a vacuum at 150 °C
for 4 h. Analysis of the activated products 3′, 5′, and 7′ by IR
spectroscopy revealed that the vibrations of the skeletal
atoms remained unchanged, although all bands were broad-
ened due to the thermal treatment and some of them even
merged (Fig. S3†), as a consequence of thermal stress.91,92
The signals of asymmetric and symmetric C–H stretching vi-
brations of methyl groups in the dmf molecule at 2998 and
2860 cm−1 disappear only in 5′, have decreased in intensity in
3′, while they are present in the form of rather sharp peaks at
2989 and 2902 cm−1 in 7′. All other bands attributed to the
CO and C–N stretching vibrations of the adsorbed dmf
molecules92,93 cannot serve as indicators since they overlap
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with the signals from the amide groups of the nicotinamide
pillars.
The complementary powder XRD patterns recorded for the
activated 3′, 7′, and 12′ materials (5′ amorphized upon
vacuumation) shed additional light on the solid state trans-
formations (Fig. S4–6†). First, they reveal the crystallinity of
all three solids, and together with the IR spectra could indi-
cate partial retention of their parent crystal lattices. For sam-
ple 3′ the coexistence of two bulk phases, the dmf loaded par-
ent 3 and the dmf free phase 4, was observed (Fig. S4†), the
latter one confirmed by single crystal structure determina-
tion. The coexistence of these two phases in the bulk explains
the observation of dmf traces in the IR spectrum of 3′. The
XRPD pattern of 7′ showed a shift to higher 2θ angles with in-
creasing temperature for the 200 and 400 reflections (Fig.
S5†). This shift indicates a significant contraction of the lon-
gest crystal lattice parameter a with temperature increase.
Since the coordination layers in 7 stack along this direction
(Fig. S1d†), the heating could result in the removal of disor-
der, orienting the dangling nia pillars perpendicular to the
coordination layer thus leading to their significant interpene-
tration into the two nearest layers. The process should be ac-
companied by the rigidification of the coordination carcass
(our recent results from ref. 65 and 66 can serve as confirma-
tion), redistribution of hydrogen bonds with the replacement
of the amide–amide NH⋯O hydrogen bonds by amide–car-
boxylate hydrogen bonds like those in the structures of 10
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Fig. 8 Thermogravimetric curves for 3, 5, 6, 7, 9 and 12.
and 11, and also similarly the capture of dmf into the gener-
ated H-bonded cages. This model explains the presence of
dmf as well-resolved C–H (CH3) νs and νas peaks in the IR
spectrum of 7′.
Upon inspection of the XRPD pattern of 12′, we observe
the same position of 002 and 011 peaks in the simulated and
experimental plots. This indicates that the longest unit cell
parameter remains constant in both forms. Most probably,
the coordination arrays are fused under such evacuation con-
ditions, making terminal coordinated water and dmf bridg-
ing molecules thus replacing the H-bonded layer with a coor-
dination layer in the same plane.
Photoluminescence properties
The emission properties of six as-synthesized Zn and Cd-
based complexes, 1, 3, 5, 7, 9 and 12, and four activated prod-
ucts, 3′, 5′, 7′ and 12′, have been investigated at room temper-
ature in the solid state. Excitation of the microcrystalline
Fig. 9 Emission spectra of 1, 3 and 12 (a) and 5, 7 and 9 (b), λexc = 337 nm.
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samples at λexc = 337 nm leads to the generation of similar
fluorescence emissions in the visible spectrum. The solid-
state emission for Cd compounds 1, 3, and 12 (Fig. 9a) is
more than an order of magnitude higher than the lumines-
cence for Zn compounds 5, 7 and 9 (Fig. 9b).
The photoluminescence (PL) emission of free ligands, ex-
cept that for iso-nia, is several orders of magnitude lower
than those observed in the complexes and does not affect the
shape of the spectra (Fig. 10).
The luminescence of the iso-nia ligand can affect the
shape of the PL spectrum of the complexes. The lumines-
cence of the iso-nia ligand affects the shapes of the spectra
of the corresponding complexes 3 and 5 in the direction of
their broadening (Fig. 9a and b). For CdIJII) complexes, bright
red photoluminescence is observed in the 550–620 nm region
(Fig. 9a). For ZnIJII) compounds, broad luminescence is ob-
served in the range of 420–620 nm (Fig. 9b). The PL spectra
of all samples have a complex structure and indicate a super-
position of several radiative processes, which is confirmed by
deconvolution of the curves using the Gaussian function. The
intensity of emission at 2.55 eV, 2.67 eV, and 2.8 eV alters
from sample to sample. For Cd, the PL intensity increases in
the order 1 < 3 < 12. Because the PL maxima in all spectra
are located in a relatively small range, 2.5–2.8 eV for CdIJII)
compounds and 2.5–3.3 eV for ZnIJII) compounds, we as-
sumed that the emissions of the complexes originate from
the intra-ligand π*–π transition. A significant red shift of this
band in contrast to that of the free ligand should be attrib-
uted to metal–ligand coordination interactions. The differ-
ences in the peak positions are the result of the dissimilar-
ities in the coordination environments of the metal centers
under the influence of the secondary ligands, which may also
include energy transfer. Furthermore, considerable enhance-
ment of the intensity for some peaks may be explained by the
increased rigidity due to the coordination of the ligand to
metal atoms and strong aromatic stacking interactions.
Two emission effects deserve more detailed consideration.
In order to obtain deeper insight into both of them the time-
dependent density functional theory (TD-DFT) approach was
used. The first phenomenon is the very intense emission of
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Fig. 10 Emission spectra for the ligands, dicarboxylic acids (a) and nicotinamides (b), λexc = 337 nm.

the iso-nia ligand in the pure state that is significantly re- dmf in a perpendicular orientation to the carboxylic plane
duced in the tested CPs 3 and 5 with iso-nia pillar. This phe- (Fig. S9†).
nomenon is rather unusual since many reported examples re- Along with the emission spectra for the as-synthesized
vealed an essential increase in the emission of coordinated solids 1, 3, 5, 7, 9 and 12, we have monitored the lumines-
ligands as a consequence of their increased stiffness in the cence properties of activated compounds 3′, 5′, 7′ and 12′. As
coordination framework. In order to understand the emission was mentioned above, both IR spectra and XRPD patterns of
quenching mechanism in 5, we optimized the lowest excited 3′, 5′, 7′ and 12′ indicated complete dmf loss for 5′ and partial
state of the monomer and found its electronic structure to be dmf removal from 3′ with the coexistence of two phases, 3
predominantly of the HOMO−1 to LUMO+3 transition. Both and 4, in the bulk. Comparison of the emission spectra of
hole and particle orbitals were localized on different ligands the as-synthesized and activated compounds revealed oppo-
(Fig. S7†), with a very small overlap between them. The site effects, a significant increase of intensity emission for 3′
resulting oscillator strength of this state was found to be c.a. and 12′, weakening for 7′, while no change was found for 5′
0.001, suggesting very weak emission from this state. This (Fig. 12).
weak oscillator strength is typical for ligand to ligand charge The emission quenching by both water and dmf is docu-
transfer state (LLCT) (Fig. S7†). In comparison, the lowest mented,7 so in cases 3′ and 12′ the increased intensity of
(emitting) state for iso-nia dimer (Fig. S8†) is brighter by the emission of the desolvated form is directly connected with
factor of 6. the increased density of chromophore ligands, iso-nia in 3′
The second phenomenon is the brightest emission of and bdc in 12′ in analogy with a recently reported case.100 It
Cd-terephthalate CP 12 amongst the six compounds studied is also in line with our observations of significantly stronger
in this work. We hypothesized that the origin of this bright emission of neat iso-nia ligand compared to the coordination
emission lies in the preferable orientation of the solvated
dmf molecules that are situated in close proximity to the
metal coordination cores (Fig. 7c). They are approximately
parallel to the bdc ligands at a certain distance affording
π–π-stacking interactions that could lead to the formation
of emitting species of the exciplex type.94–97 For quantum
chemical calculations we selected the fragment of a coordi-
nation array where termination of the polymeric chain has
been achieved via replacement of the second bdc anion by
an acetate anion coordinated to the Cd center to complete
the metal coordination core and balance out the charges.
The optimization of the second excited state for this poly-
mer fragment resulted in the proton transfer from solvated
dmf to the bdc ligand. The resulting ion pair has a strongly
emitting CT excited state as the MO pictures show (Fig. 11).
One should note that this is not just a typical exciplex,
since it involves excited state proton transfer from dmf to
carboxyl, similar to that reported in the literature.98,99 The Fig. 11 Emitting state in compound 12 presenting an exciplex of a
emitting state was found to have an n–π* character, and dmf → bdc charge transfer character, assisted by CH3–COO proton
to be 6 times brighter than that for the model with the transfer (oscillator strength: 0.058).

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Fig. 12 Comparison of the emission spectra of 3 and 3′ (a), 12 and 12′ (b), 5 and 5′ (c), and 7 and 7′ (d).
polymers it forms, 3 and 5. Ambiguous results were obtained
for 5′ since the IR spectrum shows the lack of dmf, while its
photoluminescence curve shows no change in the dmf loaded
form, 5. A more detailed study of the activated products is
ongoing.
Conclusions
A series of Zn and Cd coordination polymers with four di-
carboxylate linkers (malonate, succinate, adipate, and 1,4-
benzenedicarboxylate) and three nicotinamides (nicotin-
amide, isonicotinamide, and thionicotinamide) as single and
double pillars were synthesized. The 1D and 2D coordination
networks demonstrate the reproducibility of structural motifs
upon changing either the metal or nicotinamide ligands and
the impact of dicarboxylic ligands in the diversification of
the crystal structures. Due to the amide-pillars, all the crystal
lattices are strengthened by hydrogen bonds that affect the
crystal stability and solvent retention in the crystal lattices.
Emission of the as-synthesized and activated compounds oc-
curs in the visible spectrum and demonstrates the ligand-
based behavior typical for closed-shell d10 metal based com-
pounds. Although iso-nia is a strong individual emitter due
to its favorable intramolecular conjugation system, it lacks
emission efficiency in the reported coordination polymers.
Moreover, the linear arrangement of the binding sites in the
molecule affords centrosymmetric structures due to centro-
symmetric H-bonded supramolecular synthons, thus
prohibiting SGH activity in such solids. On the contrary, five
coordination polymers with “angular” nicotinamide and thio-
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nicotinamide ligands as single and double pillars crystallize
in the non-centrosymmetric space groups, which opens the
possibility for studying their NLO properties.
Conflicts of interest
The authors declare no competing financial interest.
Acknowledgements
The authors thank the project CSSDT 15.817.02.06F for sup-
port. A.E.M. is grateful for support by Act 211 Government of
the Russian Federation (contract no. 02.A03.21.0011) in the
part of electronic structure predictions. The authors also ac-
knowledge the National Energy Research Scientific Comput-
ing Center (NERSC), and the University of Central Florida Ad-
vanced Research Computing Center (https://arcc.ist.ucf.edu)
for providing computational resources and support.
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