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Synthesis and Characterization of New Luminescent CuX Coordinate-Ionic Hybrids

Abstract

Crystalline hybrids incorporating ionic and coordinate bonding properties have been reported to exhibit

high thermal stability as well as strong optical properties. Four new CuX (X = Cl, Br, I) hybrids were

synthesized in various reaction conditions using a cationic ligand containing multiple coordination sites,

prompting the formation of robust, highly luminescent materials. Three of these compounds exhibit bright

emission in the 550-600nm range under 365nm excitation. Two of these luminescent compounds are

crystalline, varying only in the cuprous halide chain. Structural differences seem to differ solely as a

result of halide variation, demonstrating potential for emission and bandgap tunability. High thermal

stability and apparent quantum yields make them valuable candidates for further exploration and possible

commercial use in phosphor-based solid-state lighting systems.


Introduction

The introduction of solid-state lighting (SSL) has brought newer and more efficient

technologies to consumers.1 Light emitting diodes (LEDs), the most common form of SSL, have

become popular due to their longer lifetimes and reduced energy consumption in comparison to

incandescent or fluorescent lightbulbs; 12W LED bulbs have a lifetime of around 25,000 hours,

while 15W compact fluorescent bulbs (CFLs) and 43W incandescent bulbs have lifetimes of

10,000 and 3,000 hours, respectively.2 The U.S. Department of Energys Energy Star campaign

includes a transition to SSL and connected lighting as part of its energy conservation efforts,

predicting $630 billion in energy cost savings if their SSL goals are achieved.3 As of the writing

of this report, the SSL transition is in full effect across the U.S., with white LEDs (WLEDs) of

varying temperatures commercially available in retail stores.4,5 Unfortunately, high-performing

LEDs often require the use of rare-earth elements (REEs). Commercial phosphor-converted

white LEDs (PC-WLEDs) such as those used on smartphones and bike lights (Figure 1) are

composed of a blue InGaN emitting diode coated with YAG:Ce3+, a yellow-emitting phosphor.6,7

Derivatives of YAG:Ce3+ are particularly desirable due to internal quantum yields (IQY)

exceeding 85%.6 High demand of REEs may lead to future shortages, making REE-free

phosphors highly desirable alternatives for efficient lighting.7 Of the alternatives currently being

studied, the candidates which display arguably the highest potential for future commercial use

are those classified as luminescent inorganic-organic hybrid materials.

The recognition and characterization of inorganic-organic hybrids first began in the

1990s in the form of periodically organized mesoporous materials.8,9 Eventually, research began

on functional crystalline inorganic-organic hybrid semiconductor materials, a class of very

interesting materials that combine the properties of each into a single crystal lattice, resulting in
new properties not present in either individual material.10-12 Early research revolved around

metal organic frameworks (MOFs), materials which have developed high potential for sensing,

gas separation, photovoltaics, etc.13-15 With the onset of SSL, researchers began exploring the

potential of hybrid phosphors, the first being luminescent MOFs containing metal centers with

organic emitters.16,17 Further studies led to the development of luminescent inorganic-organic

hybrid crystals featuring metal clusters. Such hybrids have been found to have tunable emission

based on various characteristics, including dimensionality, HOMO-LUMO energy, and

functional groups on organic ligands.18-22 Notably, Cu halide-based hybrids (especially CuI) have

been studied extensively due to their tendency to form clusters with potential for favorable

optical properties.23-26 The basis for these luminescent hybrids involve coordination between a

CumXm cluster of varying dimensionality (such as 1D-Cu2I2 or 2D-Cu4I4) and a lone-pair of an

N, S, or P site on an organic ligand.27,29, 33-35 Most of these phosphors, however, are limited in

their potential for commercial use due to issues such as poor robustness and being exclusively

UV-excitable.28 Attempts to increase stability have resulted in ionic compounds similar to lead

halide perovskites which, while containing inorganic and organic components, lack actual

coordinate bonds between components. Such a deficiency removes potential for metal-ligand or

halide-ligand charge transfers, resulting in luminescent quenching.30-32

A recent publication reported the synthesis of structures which combine the properties of

coordinate and ionic hybrids (Figure 2).36 Cationic functional groups on organic ligands with

multiple coordination sites prompted the formation of anionic CumXn clusters such as 1D-Cu2I42-

and 2D-Cu4I62- (Figure 3) without interacting with the cluster itself. Instead, a different N or P

atom would coordinate with the metal cluster, yielding phosphors with combined properties of

coordinate and ionic bonding, including high thermal stability and optical efficiency. In this
project, three new crystals are presented, each based on a cuprous halide cluster containing a

benzotriazole (bzt) ligand, two of which are luminescent. Alkylation of the bzt NH site allows for

the addition of a cationic amminium group, while binding with the metal ion is directed toward

one or both of the other N atoms in the triazole ring. By further adjusting the halide in the metal

cluster, there appears to be potential for optical tunability. The ionic properties of these structures

as well as the tendency of the bzt ligands to chelate yield high chemical and thermal robustness.

While more work can be done to increase blue-light excitability, this group of phosphors shows

high potential for an entire family of phosphors which could be commercial implemented.

Experimental

Materials: All materials were purchased from commercial suppliers (Alfa Aesar, Sigma-

Aldrich) and used as reagent grade. Organic syntheses were performed using standard

equipment, while crystal syntheses were carried out in 20mL glass scintillation vials.

Synthesis of [N,N-dimethyl[2-(1,2,3-benzotriazol-1-yl)ethyl]amine]+ iodide (dmbtea) (Figure

4): A mixtures of bzt (5.00 g), 1-bromo-3-chloropropane (3.14 mL, 1.0 eq) and NaOH (0.2 g, 5

mmol) was dissolved in methanol (50 mL) and refluxed at 120C for 5.5 hours. Solvent was

evaporated in vacuo at 50C, yielding 1-(3-chloropropyl)-1H-1,2,3-benzotriazole (clpr-bzt).

Clpr-bzt (0.025 mol) was fully dissolved in acetone (20 mL), and KI (5.000g) was added. This

mixture was stirred at room temperature for 2 hr. The solution was filtered, followed by addition

of trimethylamine (tma, 2 mL). White precipitate formed overnight. Crude product was filtered

and washed with acetone, then dried in vacuo.

Synthesis of 1D-CuI2(dmbtea) (1): Stock solutions of saturated KI/CuI were prepared via

sonification and filtration. Saturated stock solution (2 mL) was pipetted into a 20 mL glass

scintillation vial. Acetonitrile (2 mL) was then added slowly, followed by addition of dmbtea (1
mmol) in methanol (2 mL); this reaction is known as a three-layer synthesis. The reaction

proceeded open-air at room temperature. Yellow plate-shaped crystals formed overnight and was

extracted via filtration. The sample was left to dry for two days after washing with methanol and

distilled water. This three layer synthesis was utilized in a previous paper36 with exception of a

saturated first layer; this modification was implemented to further encourage cluster formation,

accelerate crystallization and increase yield.

Synthesis of 1D-CuBr2(dmbtea) (2): Stock solutions of saturated KBr/CuBr were prepared via

sonification and filtration. Saturated stock solution (2 mL), acetonitrile (2 mL), and dmbtea (1

mmol) in methanol (2 mL) were pipetted into a 20 mL glass scintillation vial, identical to the

synthesis of 1. The reaction proceeded open-air at room temperature. Yellow rod-shaped crystals

formed overnight and were extracted via filtration. The sample was left to dry for two days after

washing with methanol and distilled water.

Synthesis of Unknown CuBr-dmbtea powder (3): Synthesis of compound 3 was identical to

that of compound 2, however, ethanol was used instead of methanol to dissolve dmbtea. A green

powder formed overnight and was collected via filtration. Single crystal x-ray diffraction could

not be performed due to lack of crystal formation.

Synthesis of CuxCly(dmbtea)z (4): Stock solutions of saturated NaCl/CuCl were prepared via

sonification and filtration. Saturated stock solution (4 mL), acetonitrile (2 mL), and dmbtea (1

mmol) in 2 mL methanol were pipetted into a stainless steel autoclave for hydrothermal

synthesis. The vessel was kept at 180C under autogenous pressure for 24 hours, forming

transparent, rod-shaped crystals. The sample was left to dry for two days after washing with

methanol and distilled water. Single crystal x-ray diffraction could not be performed due to time

constraints, thus the structural formula has not been determined.


Single Crystal X-Ray Diffraction (SCXRD): SCXRD measurements and structure solving

were performed on compounds 1 and 2 by a collaborator due to lack of equipment at the research

facility. A D8 goniostat equipped with a Bruker PHOTON100 CMOS detector at the

collaborators facility were used to collect single crystal data using synchrotron radiation. The

structures were solved by direct methods and refined by full-matrix least-squares on F2 using the

Bruker SHELXTL package.

Powder X-Ray Diffraction (PXRD): PXRD patterns were collected by Competition Entrant on

a Rigaku Ultima IV with Cu K radiation ( = 1.5406 ) at room temperature. A 2 range of 3

40 was used with a scan speed of 2 min-1 at an operating power of 40 kV and 44 mA.

Photoluminescence (PL): PL measurements were performed on a Varian Cary Eclipse spectrometer

at room temperature. Powder coatings on non-emissive glass slides were measured using a

preliminary test excitation of 365nm. Peak emissions found at 365nm excitation were then measured

using a 350-450nm excitation spectra.

UV-Vis diffuse reflectance: Optical diffuse reflectance measurements were performed on a

Shimadzu UV-3600 spectrophotometer. Data was collected with a wavelength range of 350-700

nm. Crystalline samples were ground into powder and distributed evenly between calibrated

quartz slides for measurement. The optical bandgap of both compounds was estimated by

transforming reflectance data to the Kubelka-Munk function, /S = (1-R)2 /2R ( = absorption

coefficient, S = scattering coefficient, R = reflectance). Figures display data transformed to a

sixth degree polynomial for ease of display in Microsoft Excel.

Thermogravimetric Analysis (TGA): TGA measurements were performed on a TA Q5000

analyzer. Samples were loaded onto a platinum pan and heated with a ramp rate of 10 C min-1

from 30 C to 600 C under nitrogen flow (50 ml min-1).


Design of LED Bulbs: LED tests were performed by covering high-powered 3.1V 450-460nm

DEMASLEDs with Scotch double-sided tape, then coated with commercial and synthesized

phosphors. Pictures were taken using an iPhone SE camera.

Results and Discussion

Ligand Synthesis: This report extends the design from a previously mentioned publication by

using longer alkyl halides to create similar bzt ligands.36 Ligands with alkyl chains of varying

length were also studied; the use of dmbtea in three-layer crystallization was unique in its

relatively high yield and reactive spontaneity with both CuI and CuBr at room temperature.

Crystallization conditions for other ligands with varying alkyl chain lengths have yet to be found.

The synthesis of dmbtea is shown in Figure 4. The H1NMR spectrum of clpr-bzt (Figure 5) was

taken before vacuum dry, resulting in the presence of methanol peaks. KI was used to prepare the

ligand as a salt to be dissolved in methanol instead of an ion in solution for facile storage and

synthesis.

Structure Analysis: The previously reported phosphor36 using a bzt-based ligand, 1D-

Cu4I6(tpp)2 (bttmm)2 (Figure 6b), was synthesized via a 0D precursor (triphenylphosphine = tpp,

[(3H-indazol-3-yl)methyl]trimethylazanium = bttmm). Each Cu+ ion bonded once with each

ligand molecule. Compounds 1 (1D-Cu2I3(dmbtea)), 2 (1D-Cu2Br3(dmbtea)), 3 (hypothesized to

be 1D-Cu2I3(dmbtea)) and 4 (formula unknown, CuxCly(dmbtea)z) were all synthesized without

the use of a precursor, thus dmbtea is the sole ligand present in all structures. A quasi-chelating

effect is observed in compounds 1-3; two nitrogen atoms from the triazole ring of dmbtea

coordinate to neighboring Cu+ ions on a 1D-Cu2X3- chain (Figure 6a). The Cu2X3- cluster has

not been previously reported; extensive studies have yet to be performed on the effects of ligand

structure on cluster type and dimensionality. Evidently, the formation of this chain was only
possible due to the lack of the precursor; the two nitrogen bonding sites occupy what would

otherwise be a halide in a Cu2X2 neutral dimer. Compound 1 crystallizes in the monoclinic

crystal system, while compound 2 is orthorhombic. The differences in cell volume and

measurements are believed to be solely the result of the increased size of the iodide anion, as the

compounds share the same dimensionality and bonding patterns with dmbtea. Cell angles

indicate that both structures contain considerably less stress than 1D-Cu4I6(tpp)2 (bttmm)2,

consistent with increased thermal stability (compounds 1 and 2 decompose around 250C, while

1D-Cu4I6(tpp)2 (bttmm)2 begins decomposing at 200C)36. Cu-L bond lengths differ for each

bidentate N atom, measured to be 2.109 /2.060 for compound 1 and 1.987 /2.057 for

compound 2, accounting for the differences in crystal systems and unit cell measurements

between compounds. Unit cell diagrams of compounds 1 and 2 are shown in Figure 7. Complete

crystal dimensions are displayed in Table 1.

The PXRD patterns for compounds 1-4 are shown in Figure 8a-d. Compounds 2 and 3

exhibit identical low-angle peaks of different intensity. While the structure of 3 has not been

determined, solvent molecules disruption during crystallization may have caused the ligand to

coordinate at different positions or angles, resulting in a different colored compound. The overall

structure of compound 3 is likely very similar to compound 2, as the two compounds have nearly

identical thermal and optical properties.

Compounds 1 and 2 were also kept at 80C under autogenous pressure for 10 days with

PXRD measurements taken before and after; low angle-peaks remained consistent for both

measurements (Figures 9a-b and 10a-b). This is promising for SSL use, as lifetimes of cheaper

phosphors are often a major concern when considering commercial use. Further tests may

include moisture and higher temperature stability; more importantly, these tests cannot lead to
luminescent quenching if the compounds are to be explored for commercial use. Visibly and

structurally, both compounds seem to exhibit stability through the 10-day thermal test, but

further tests will be held off until IQY measurements can be performed.

Compounds 1-3 also exhibit high thermal stability under extreme conditions, with

negligible decomposition until around 250C, shown in the TGA curves (Figure 11). In general,

the decomposition of hybrid phosphors equates to the evaporation of organic ligands. For hybrids

with neutral components, ligand loss occurs due to cleavage of a Cun+-L coordinate bond. In

these combined coordinate-ionic structures the vaporizing component is hypothesized to be a salt

formed by the cationic ligands and halide anions. Both the Cun+-L and Cu-X bond need to be

cleaved for this to occur. Enhanced thermal stability may be derived from extra energy necessary

for cleavage of the Cu-X bond.

As mentioned earlier, the structure of compound 4 was not determined due to time

constraints. However, we hypothesize that a coordinate bond is not present in the structure, as it

does not exhibit visible emission under UV, blue, or 254nm light. Compound 4 also exhibits

negligible decomposition through 600C, shown in the TGA curve (Figure 11), implying high

bonding energies. It is hypothesized that the crystal may be purely an ionic structure. This is not

surprising due to the bonding radius of the chloride anion (~99pm) compared to those of bromide

(~114pm) and iodide (~133pm),37 resulting in a tighter metal chain and reduced space for a

ligand to coordinate. The lack of coloration may also indicate the crystals ionic nature (although

it cannot be used as the sole identifier); crystal field theory implies the d-orbitals of the Cu ions

may still be degenerate, having not rearranged to accommodate a coordinate bond.

Optical Properties: The room temperature photoluminescent (PL) spectra of compounds 1-3 are

shown in Figure 12. Compound 1 exhibits strong yellow emission (555 nm), visibly blue-shifted
from the orange emission of compound 2 (595 nm). Peak emission differences between the two

compounds is favorable for lighting applications, as it demonstrates emission tunability which

can be used to produce white light of different temperatures (i.e. warm and cool white

light are produced using different intensities of red and blue light)38. Compound 1 exhibits

significantly brighter emission. Using the Kubelka-Munk function from diffuse reflectance

measurements, optical bandgap for compounds 1 and 2 are estimated to be ~2.35 eV and ~2.46

eV, respectively (Figure 13), which may imply cluster-centered (C-C) or halide-ligand (X-L)

centered transitions being responsible for emission, consistent with the electronegativity of each

halide (I- < Br-). Density functional theory (DFT) measurements may be conducted in future

studies to confirm this observation. Photoluminescence lifetime measurements are necessary to

hypothesize the type of transition (e.g. singlet-singlet, singlet-triplet) and for complete Jablonski

analysis, however, the consistency of both structures in nearly every aspect aside from formulaic

differences leads to the belief that an X-L transition is a strong hypothesis.

While IQY data could not be obtained due to equipment malfunctions, relative excitation

spectra were taken using the Varian Cary Eclipse spectrometer (Figure 14). Separate emission

spectra under 455nm excitation are also shown in Figure 12. Compound 1 exhibits strong 555nm

emission under 350-460nm excitation. However, compound 2 exhibits 595nm emission under

excitation less than 400nm, dropping off at lower energies. This may be a result of the higher

bandgap and structural composition of compound 2; more energy is required for excitation to

occur for a hypothesized bromide-ligand transition. LED and UV images of compounds 1, 2, and

YAG:Ce3+, the commercially favored yellow phosphor, are shown in Figures 15 and 17.

Microscope images of compounds 1-4 are shown in Figure 16. Optical properties of compounds

1-4 are summarized in Table 2.


Conclusions

Four new compounds were synthesized with the intent of creating highly stable and

luminescent compounds by combining coordinate and ionic bonds. Three of these compounds,

two unique (1 and 2), exhibited strong optical properties, including strong luminescence and

bandgap tunability based on formulaic halide variation. Differences between copper iodide and

copper bromide structures appear to be purely a result of halide variation, showing promise for

bzt ligand types to be tunable using discrete variables. Further structural and thermal analyses

were performed revealing high robustness throughout, hypothesized to be a result of the quasi-

chelating ligand, a new phenomenon which was possible due to the direct crystallization of CuX

with the ligand as opposed to the use of a precursor. Optical patterns were analyzed and used to

present a strong hypothesis for the transition type without the use of DFT calculations.

Tunability based on halide variation shows promise for producing commercials white LEDs of

different temperatures. Prototype LEDs were created and photographed; the CuI based structure

exhibits high apparent IQY and seems comparable to YAG:Ce3+. This study represents a

benchmark for expansion of bzt ligand exploration with the potential to create family of

structures containing bzt-based ligands with varying alkylated chains, possibly resulting in a

wider range of bandgap and luminescent tunability.

Future Work and Acknowledgements

While this report is a comprehensive analysis of new materials, it is incomplete. Due to

my lack of experience, significant time was spent learning analyses procedures and lab safety.

Additionally, while Dr. Wei Liu, my mentor, and other lab members provided invaluable

guidance, I am still learning the basics of organic syntheses and reaction design. Mentioned first
in the experimental section, I would like to reiterate thanks to Dr. Liu for helping facilitate ligand

proposals. Aside from time constraints, lack of equipment at the research facility was another

limiting factor. SCXRD and IQY data could not be readily collected. Additionally, tasks such as

DFT and HOMO-LUMO measurements using advanced software such as Gaussian 9 are

currently beyond my understanding. Such measurements could be used to determine the

transition responsible for emission. With time and higher education, I would gladly take the

opportunity to review this report with expanded knowledge of organic chemistry and hybrid-

specific analyses.

As mentioned earlier, compounds 2 and 3 exhibit little to no emission under 455nm light.

The orange emission of these two phosphors is desirable for white light temperature tunability,

so future work with 1D-CuBr chains may be focused on decreasing the bandgap. Determining

which transitions are responsible for emission is important in formulating a new approach,

making DFT measurements ever more valuable. Developing synthesis conditions for a

luminescent CuCl crystal is also still in progress.

Current coordinate-ionic hybrid structures utilize cationic ligands, prompting anionic

cluster formation. Dr. Liu recently came across a publication which reported CuX-tetrazolide

crystals, featuring the tetrazolide anion coordinating with cationic clusters.24 After reading the

publication, I thought it would interesting to explore potential for other reverse coordinate-

ionic hybrid structures using five-member heterocyclic rings. While pyrrole proved to be inert,

some luminescent powders were obtained using 1H-imidazole, methyl-imidazole, and 1H-

triazole via hydrothermal syntheses. Structures could not be determined for these compounds due

to lack of single crystal formation. Sulfur-containing organic compounds may have higher
potential for forming anionic ligands due to having higher pH values than nitrogen-containing

compounds. Preliminary tests have been run on a few compounds with no results.

Cluster formation patterns are also of interest. As of this report, there seems to be little

correlation between the organic ligand and the dimensionality of the anionic CuX cluster. The

Cu2X3- cluster is a new orientation. The dimensionality of clusters is important in that it denotes

how many Cu ions are available as bonding sites.


Figures and Tables:

Fig. 1. Fig. 3 Figure 1 A commercial


white LED bike light.
The yellow phosphor
coating, likely
YAG:CE3+, is clearly
visible.40
Figure 2 Graphical
representation of
combining coordinate
and ionice bonds into a
Fig. 2 single cohesive crystal
lattice.39
Figure 3 From top to
bottom, ball-and-stick
models of Cu2X3-,
Cu4X62-, and Cu6I82-
chains.39

bzt bcp clpr-bzt dmbtea

Figure 4 Synthesis of dmbtea via clpr-bzt precursor. Isomers of clpr-bzt were not separated, as I was
allowed to run only basic columns as learning experience; more complex columns were deemed unsafe.40

Figure 5 H1NMR (300


7.9
3.2 MHz, DMSO) spectrum
7.3 of clpr-bzt after 2 d.
rest. Vacuum drying
was not performed due
4.2
to malfunction of
MeOH(?) DMSO
equipment.40
a. b. c.

Figure 6 Solved structure for (a) compounds 1-2, hypothesized structure for 3. (b) Previously reported
crystal containing bzt ligand and tpp.36 (c) Example bzt ligands as ionic salts. White = C, blue = N, cyan =
Cu, pink = halide, green = P. H atoms have been omitted for clarity.36,39

Figure 7 Unit cell diagrams of compound 1 (left) and compound 2 (right).39

Fig. 8 Fig. 10

d.

c. b.

b.

a.
a.

Fig. 9
Figure 8 PXRD patterns for (a) compound
1. (b) compound 2. (c) compound 3. (d)
compound 4.40
Figure 9 PXRD patterns for (a) compound
b. 1 (b) compound 1 after 10 d. at 80C.40
Figure 10 PXRD patterns for (a)
compound 2 (b) compound 2 after 10 d. at
80C.40
a.
Fig. 11 Fig. 13

Fig. 12 Fig. 14

Figure 11 TGA curves for compounds 1-4.40


Figure 12 Photoluminescence spectra for compounds 1-3 for select excitation wavelengths.40
Figure 13 UV-vis spectra transformed into KM-function plotted against energy for compounds 1-3.40
Figure 14 Excitation spectra for compounds 1 and 2 at 555nm and 595nm, respectively.40

a. b. c. d.

Figure 15 3.0-3.2 V 455nm DEMSLED coated with (a) no compound. (b) YAG:Ce3+. (c) compound 1. (d)
compound 2.40
a. b.

Fig. 17

Figure 16 Microscope images of


(a) compound 1. (b) compound 2.
(c) compound 3. (d) compound 4.40
Figure 17 From left to right,
YAG:Ce3+, compounds 1, 2 under
UV irridation.40
Fig. 16 c. d.

Table 1 Crystal data for compounds 1, 2, and previously reported luminescent hybrid with bzt-based
ligand.36,40

(C12H19N3Cu2I3)

(C12H19N3Cu2Br3)

Table 2 Summary of optical and thermal properties for compounds 1-4.40


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39) Diagram created by Dr. Wei Liu.

40) Diagram created by Alexander Liu.