A XXXV-a CONFERINŢĂ NAŢIONALĂ DE CHIMIE 2018

XXXV-th ROMANIAN CHEMISTRY CONFERENCE

THE HIGH AFFINITY OF SMALL-MOLECULE ANTIOXIDANTS FOR

HEMOGLOBIN AND MYOGLOBIN

Cristina Puscas1, Luana Radu1, Francisco Carrascoza1, Augustin Mot1, Diana Amariei1,
Oana Lungu1, Florina Scurtu1, Paula Podea1, Raluca Septelean1, Alina Matei1, Mihaela
Mic2, Radu Silaghi-Dumitrescu1
1. Department of Chemistry, Babes-Bolyai University, 1 MihailKogalniceanu street, Cluj-Napoca
400084, Romania
2. Department of Molecular and Biomolecular Physics, National Institute of Isotopic and Molecular
Technologies, 400293 Cluj-Napoca, Romania
*email: cbischin@chem.ubbcluj.ro

Reported here are Michaelis-Menten data according to which hemoglobin has high
affinity for a wide range of exogenous small-molecule antioxidants such as caffeate, gallate,
rutin, quercetin, epicatechin, luteolin, 3-hidroxiflavone and 3,6-dihydroxiflavone.Furthermore,
1 13
H-NMR and C-NMR spectrareveala fast dynamic effect or the existence of multiple binding
sites of these antioxidants on myoglobin. Fluorescence and ICT measurements also suggest high-
affinity dynamic binding with a key role for hydrogen bonding and van der Waals forces.
Docking calculationsallow for identification of binding siteson globinsfor the antioxidants
investigated here, in all cases with affinities in the sub-millimolar range, in good agreement with
the experimental data. As was proposed before1, Tyr42 is shown to be involved in the binding of
three substrates studied here. Additionally, Tyr 145, Tyr 35 and other redox-active
aminoacids(mainly Trp) are found at the binding sites of antioxidants on hemoglobin and/or
myoglobin. Thesedata may bear physiological relevance in terms of the increasingly versatile
dietary patterns of humans onnon-endogenous small antioxidants, as well as in understanding the
manners in which the effect of oxidative stress may be reduced in cases where the stress-related
reactivity of globins is important, such as in hemoglobin-based oxygen carriers (HBOC).

Acknowledgment:Funding from the Romanian Ministry for Education and Research (grant PN-II-ID-PCE-2012-4-
0488 and PN-III-P4-ID-PCE-2016-0089) is gratefully acknowledged.

References: 1. Reeder BJet al. J Biol Chem. 2008;283(45):30780.

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NOVEL HETEROTRISPIN COMPLEXES

A. A. Patrascu a,b, S. Sorianoc, M. G. F. Vazb and M. Andruha
a
Faculty of Chemistry, University of Bucharest,Inorganic Chemistry Laboratory,Bucharest, Romania
b
Instituto de Química, Universidade Federal Fluminense, Niterói, Rio de Janeiro, Brazil
c
Instituto de Física, Universidade Federal Fluminense, Niterói, Rio de Janeiro, Brazil
andrei_alunel@yahoo.com

Heterospin complexes containing three different paramagnetic centers are of high interest
in molecular magnetism [1]. Such complexes are still rare because of the synthetic difficulties
that must be overcome by chemists.
In this work we present two families of heterotrispin complexes containing: a) two
different paramagnetic metal ions and a paramagnetic organic radical; b) three different
paramagnetic metal ions (ReIV, CoII/NiII/CuII, LnIII).
The nitronyl-nitroxide radicals played a very important role in the history of molecular
magnetism [2]. We recently described a novel family ofend-off bicompartmental ligands bearing
a nitronyl-nitroxide arm, which are very useful in designing various heterospin molecular
systems. These ligands can selectively interact with 3d and 4f metal ions, leading to 2p-4f, 2p-3d,
and 2p-3d-4f complexes [3]. By employing new chiral nitronyl-nitroxide radicals, we obtaineda
2p-3d-4fheterotrispin structural prototype, having the radical as a bridge between 3d and 4f metal
ions through only one O atom, creating a direct connectivity through the three different spin
carriers. The CoDy-R(+)rad complex (Figure 1a) exhibits a high blocking temperature of 28 K.
We currently employ a rational synthetic approach towards 3d-nd-4ftrimetallic
complexesthat consists of self-assembly processes involving presynthesized 3d-4f heteronuclear
complex cations [4] anda Re(IV)metalloligand.Two families of -3d-4f complexes have been
obtained: hexanuclear clusters (Figure 1b) and zigzag 1-D coordination polymers.

a) b)
Figure 1. Perspective views of CoDy-R(+)rad compound and the hexanuclear cluster Re2Co2Dy2

[1] M. Andruh, Chem. Commun.2018,54, 3559.

[2] A S. Demir, I.-R. Jeon, J. R. Long and T. D. Harris, Coord. Chem. Rev. 2015, 289-290, 149.
[3] A. A. Patrascu, S. Calancea, M. Briganti,S. Soriano,A. M. Madalan, R.A. Allão Cassaro,A. Caneschi, F.
Totti, M. G. F. Vaz, M. Andruh, Chem. Commun.,2017, 53, 6504.
[4] M. Andruh, Chem. Commun., 2011, 47, 3025.

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REȚELE COORDINATIVE CARBOXILICE ALE Co(II), Cd(II) și Zn(II) DECORATE CU

LIGANZI NICOTINAMIDICI: SINTEZĂ, PROPRIETĂȚI FIZICO-CHIMICE.
D. Chișca,1,2 L. Croitor,1 O. Petuhov,3 Ed.B. Coropceanu,2,3 M. S. Fonari1
1
Institute of Applied Physics, str. Academiei 5, MD2028, Chișinău, R. Moldova
2
Tiraspol State University, str. Iablocikin 5, MD2069, Chișinău, R. Moldova
3
Institute of Chemistry, str. Academiei 3, MD2028, Chișinău, R. Moldova

Activitatea de cercetare în prezent este orientată spre proiectarea dirijată și construirea

polimerilor coordinativi cu liganzi micști, cum ar fi blocurile de construcție formate din liganzi de
tip bipiridinici și policarboxilat. Această strategie este utilizată pentru obținerea rețelelor rigide care
pot fi aplicate în adsorbția gazelor și cataliza eterogenă, dar și pentru adsorbția fizică a CO2 în rețele
cristaline.
Polimerii coordinativi (PC) care își păstrează cristalinitatea în rezultatul reacțiilor de schimb
dintre anionii sau cationii oaspeți, reacțiilor de substituție la centrul metalic, prin transformare
monocristal în monocristal MC-MC, prezintă o nouă clasă de materiale care pot fi considerate
recipiente moleculare. Astfel de reacții sunt importante pentru cataliza eterogenă și pot fi utilizate
pentru obținerea sistemelor îmbunătățite de adsorbție a gazelor. Luând în considerare aplicabilitatea
pe larg a PC în diferite domenii de activitate umană, este foarte important de a găsi metode optime
de sinteză a polimerilor coordinativi cu proprietăți preconizate.
În lucrarea de față, vom descrie sinteza, structura și proprietăţile fizico-chimice ale polimerilor
coordinativi 1D, 2D și 3D ai Co (II), Cd (II) și Zn(II) ce au fost obținuțidin sistemele: acid
dicarboxilic-ligand neutru nicotinamidic [1-6]. Vor fi explicate transformările monocristal în
monocristal induse termic ce au loc în astfel de rețele și fenomenele ce au loc ca rezultat al acestor
transformări precum: reconstruirea rețelelor coordinative, schimbarea culorii, modificări în poliedrul
de coordinare al metalului precum și în spectrele de absorbție și emisie. Schimbările structurale sunt
explicate cu ajutorul difracției razelor X pecristal și pulbere.
[1] Chisca D. et al., CrystEngComm, 2016, Vol.18, 384-389.
[2] Chisca D. et al., CrystEngComm, 2016, Vol.18, 38-41.
[3] Chisca D. et al., Cryst. Growth Des., 2016, Vol.16, 7011−7024.
[4] Croitor L. et al., J. Mol. Str., 2017, Vol. 1137, 136-141.
[5] Croitor L. et al., CrystEngComm, 2012, Vol. 14, 3750-3758.
[6] D. Chisca, et al., CrystEngComm, (2018), 20, 432-447.

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CONTRIBUȚII LA VALORIFICAREA ELEMENTELOR UTILE DIN CENUȘILE

PIRITICE DE VALEA CĂLUGĂREASCĂ
Jack Goldstein 1 , Liana Oşanu 2 , Giulia Slavic 1 , Mirela Miclean 3
1
S.C. CMC Chimie S.R.L. , Str. Principală nr. 1, sat Cărbunar , jud. Maramureş
2
A.C. Helcor S.A. Baia Mare , Str. V. Babeş nr. 50
3
Administrația de Apă Someș – Tisa , str.Vânătorului nr. 17 , Cluj-Napoca

În lucrare se prezintă o tehnologie de dezarseniere a cenușilor rezultate la desulfurarea piritelor ,

concomitent cu extragerea aurului , argintului şi a unui reziduu feros , prelucrabil la obţinerea fierului
metalic .
Tehnologia stabilită la nivel laborator şi verificată la nivel pilot constă în tratarea la 60 – 800 C a
cenuşilor cu o soluţie conţinând 30 g/l NaOH şi 60 g/l Na2S timp de 3 ore când arseniul trece în soluţie ,
de unde prin acidulare la un pH de 0,5 – 1,5 se separă sub formă de As 2S3 . Reziduul filtrat cu un conţinut
de 0,03 – 0,04 % As , 0,9 – 2,0 g/t Au şi 25 – 35 g/t Ag este supus extracţiei metalelor nobile prin solvirea
lor într-o soluţie de tiosulfat de amoniu 25 – 30 g/l la pH 10 – 11 în prezenţa catalizatorului amină cuprică
( 0,1 g/l Cu ) provenită din recirculare . Reacţia se realizează prin amestecare la un raport solid – lichid de
1 – 1,5 sub barbotare de aer la 15 – 25 0C timp de 3 - 4 ore . Suspensia se filtrează sub vid . Reziduul
rezultat şi spălat cu un conţinut de 55 – 60 % Fe , 8 – 12 % H2O şi lipsit practic de metale neferoase şi
nobile este utilizabil ca materie primă în metalurgia fierului .
Soluţia filtrată cu un conţinut de 0,9 – 1,3 mg/l Au şi 10 – 15 mg/l Ag este recirculată la operaţia
de solvire a cenuşilor piritice până la obţinerea unei soluţii cu un conţinut de minim 5 mg/l Au şi 50 – 80
mg/l Ag şi supusă unei operaţii de electroliză cu obţinerea unui cement de cupru , aur şi argint .
Electroliza soluţiei se realizează în cuve din polietilenă , anodul şi catodul din oţel aliat , la o densitate de
curent de 200 – 250 A/m2 , o temperatură de 15 – 20 0C şi o durată de 8 – 10 ore . Suspensia rezultată
dupa electroliză este filtrată . Soluţia cu un conţinut de 3 – 4 mg/l Au , 40 – 60 mg/l Ag şi 25 – 30 g/l
(NH4)2S2O3 este corectată la 0,1 g/l Cu şi recirculată la operaţia de solvire a aurului şi argintului .
Cementul de Cu-Au-Ag ce conţine 50 – 80 % Cu , 1 – 10 % Au şi 5 – 30 % Ag este solubilizat în apă
amoniacală timp de 1 – 2 ore la o temperatură de 15 – 20 0C când cuprul trece în soluţie sub formă de
amină cuprică . Suspensia se filtrează . Soluţia de amină cuprică – catalizatorul procesului – este
recirculată la solvirea cenuşilor , iar cementul de Au – Ag este topit alcalino-reducător la 1.200 0C
obţinându-se aliajul Au – Ag ( aliaj dore ) .
Randamentul de valorificare a metalelor sunt : 86 – 93 % Au , 75 – 80 % Ag şi
95 – 99 % Fe .

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AI-FORECAST PROJECT (PN-III-P4-ID-PCE-2016-0299) BETWEEN PREDICTION OF

THE AEROSOL CHEMICAL COMPOSITION AND INTEGRATION OF CERNESIM’S
INFRASTRUCTURE IN A EUROPEAN CONTEXT
Cecilia Arsene,1,2,* Romeo Iulian Olariu1,2
”Alexandru Ioan Cuza” University of Iasi, Faculty of Chemistry, 11 Carol I, Iasi, 700506, Romania
1
2
”Alexandru Ioan Cuza” University of Iasi, Integrated Center of Environmental Science Studies in the North
Eastern Region (CERNESIM), 11 Carol I, Iasi, 700506, Romania
*Corresponding author: carsene@uaic.ro
Exposure to aerosols exerts a negative impact on human health and, moreover, aerosols affect
climate and the environment. The effects strongly depend on the composition and sources of atmospheric
aerosols in the form of particulate matter with aerodynamic diameter below 2.5 µm, PM 2.5, or 10 µm,
PM10. Since air pollution at a global level continues to harm people’s/environment health, significant
work is still needed to fill the knowledge gaps and to coordinate mitigation approaches in many world-
wide areas where such actions are lacking.
AI-FORECAST (Assessing the Anthropogenic and Biogenic Emissions Impact on Atmospheric
Urban Fine Organic Particles in Eastern Romania. Solving the Challenge of the Aerosols Missing Mass
as a One Step Forward Tool) project addresses important challenges in the European Union’s 7 th
Environment Action Programme where the EU 2020-2050 vision covers aspects as climate change and
societal challenges related to human-well beings.
Research infrastructure available at CERNESIM-UAIC and AMOS (Air Quality Monitoring
Station) unit (http://erris.gov.ro/cernesim.uaic.ro) plays an important role in addressing the research and
innovation tasks of the project. For Iasi urban area it has been estimated that within the aerosol mass
concentration the ionic mass brings contribution as high as 40.6 %, with the rest being unaccounted yet1 .
Moreover, the CERNESIM-AMOS-AI-FORECAST triangle contributed to the integration of the UAIC
team in a European context, as active part within the EUROCHAMP-2020 (730997) and COLOSSAL
(Chemical On-Line cOmpoSition and Source Apportionment of fine aerosols, CA16109) programs.
Acknowledgements: The authors acknowledge the financial support provided by UEFISCDI within the PN-III-P4-ID-
PCE-2016-0299 (AI-FORECAST) and also the European Union's Horizon 2020 research and innovation programme,
through the EUROCHAMP-2020 Infrastructure Activity Grant (grant agreement No 730997) and Chemical On-Line
cOmpoSition and Source Apportionment of fine aerosoLs COLOSSAL grant (CA16109).
References
1. Galon-Negru, A.G., Olariu, R.I., Arsene, C., Chemical characteristics of size-resolved atmospheric aerosols in Iasi,
north-eastern Romania: nitrogen-containing inorganic compounds control aerosol chemistry in the area, Atmospheric
Chemistry and Physics, 18, 5879-5904, 2018.

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XXXV-th ROMANIAN CHEMISTRY CONFERENCE

SINTEZA ȘI DESIGNUL MOLECULAR AL COMPLECȘILOR V(II,IV), FeIII, CoII, CuIIși ZnII CU

2,6-DIACETILPIRIDINĂ BIS((IZO)NICOTINOILHIDRAZONE)
Ion Bulhac*, Olga Danilescu
Institutul de Chimie, str. Academiei,3, Chișinău, MD-2028,R.Moldova
*ionbulhac@yahoo.com
Bazele Schiff sunt utilizate pe larg în sinteza compușilor coordinativi datorită diversității modului de
coordinare a acestora și designului complecșilor formați în funcție de natura metalului. 2,6-Diacetilpiridina
condensează relativ ușor cu hidrazidele acizilor izonicotinic și nicotinic în raport molar de 1:2, formând 2,6-
diacetilpiridină bis(izonicotinoilhidrazona) (H2L1)(1)și 2,6-diacetilpiridină bis(nicotinoilhidrazona)(H2L2)
(2). Acestea coordinează la metal, de regulă, ca liganzi pentadentați cu setul de atomi donori
N3O2.Compușii FeIII,majoritatea celor de CoII și un număr mai mic de complecși ai VII,IV reprezintă compuși
mononucleari cu poliedre de coordinare în formă de bipiramidă pentagonală, baza căreia o constituie 1 sau 2
în formă cetonică sau enolică, moleculară sau mono-/bis-deprotonată, iar vârfurile bipiramidei le constituie
liganzii H2O, NCS-, N3-,SO42- ș.a., coordinați monodentat. Astfel, metalele respective generează compuși
coordinativi moleculari sau ionici: [CoII(H2L)X2], [CoII(HL)XA], [CoII(L)A2], [FeIII(H2L)A2]X3,
[VII(L)(H2O)2], [VIV(=O)(H2L)(SO4)] (A = molecule neutre de solvenți; X = anioni ai acizilor
anorganici). Vanadiul(II) și cuprul(II) formează cu 1 și 2 compuși dinucleari cu structură elicoidală, în care
fiecare moleculă de ligand coordinează la ambii atomi de metal, generândcompuși ionici ce conțin cationi
complecși: [VII2(HL1)2]2+, [VII2(H2L2)2]4+, [CuII2(H2L1)2]4+. Cuprul poate forma de asemenea complecși cu
nuclearitate mai înaltă, tetranucleari - [Cu4(HL2)4(OH)2]2+. Utilizând metoda de sinteză solvotermală, s-a
constatat că 1 și 2 coordinează, de regulă, în calitate de liganzi bis-deprotonați cu antrenarea în acest proces
și a atomilor de azot heterociclici de origine hidrazidică, ceea ce conduce la realizarea structurilor
polimerice și supramoleculare. Astfel de structuri sunt mai mult caracteristice pentru
zinc(II):{[Zn(L )]∙0.2EtOH·0.4H2O}n, {[Zn(L )]·0.5dmf·H2O}n,dar se întâlnesc și pentru cobalt(II)-
1 2

{[Co(L2)]∙0.7dmf∙0.7H2O}n. Agenții de coordinație 1 și 2,și unii complecși ai acestora, manifestă diferite

proprietăți utile: luminescență(1, 2 și compușii polimerici ai zincului cu acești liganzi), stimulatori ai
sintezei componentelor antioxidante la cultivarea microalgei Porphyridium cruentum(complecși ai CoII cu
2), stimulatori ai sintezei ficobiliproteinelor de către cianobacteria Nostoc linckia și inhibitori ai
enzimogenezei la cultivarea micromicetei Aspergillus niger CNMN FD 10(compuși ai FeIII cu 1 și 2).

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PLATINUM COMPLEX FORMATION ABILITY AND STABILITY CONSTANTS OF

THIOSEMICARBAZONE LIGANDS

Madalin Damoc1, Alexandru Stoica1, Ionela Grecu1, Mirela-Fernanda Zaltariov2, Maria

Cazacu2
"Al. I. Cuza" University, Faculty of Chemistry, Bulevardul Carol I nr. 11, Iași 700506, Romania
1

2
"Petru Poni" Institute of Macromolecular Chemistry, Aleea Grigore Ghica Voda 41A, Iasi
700487, Romania

Salicylaldehyde and pyridine-2-carbaldehyde thiosemicarbazones and S-methyl-

isothiosemicarbazones have been prepared and characterized (Figure 1). The stoichiometry and
stability of platinum complexes of these ligands have been determinated by UV-vis spectroscopy
in aqueous solutions of methanol, dimethylformamide and acetonitrile.

OH OH N N

N S N S N S N S
HN N HN N
NH2 NH2 NH2 NH2
GI_1 GI_2 GI_3 GI_4

Figure 1. The structure of thiosemicarbazone ligands used in complexation of Pt4+ ions

The stability constants of H2PtCl6 and K2PtCl6 were calculated by using the Benesi – Hildebrand
equation. The values of the stability constants were found to depend on the polarity of solvents as
well as by platinum salt and the structure of ligands (logβ=2.84…4.057 M-1).
Stoichiometry of the thiosemicarbazones/platinum was determined by Job’s method and the results
proved the formation of 1:1 complexes.

Acknowledgements: This work was supported by a grant of the Romanian Ministery of Research and
Innovation, CCCDI - UEFISCDI, project number PN-III-P1.2-PCCDI-2017-0185/76PCCDI/2018, within
PNCDI III.

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TETRAKIS(4-CARBOXYPHENYL)STANNANE – A NEW ORGANOMETALLIC

TECTON FOR THE CONSTRUCTION OF COORDINATION POLYMERS
Alexandru Sava1, Teodora Mocanu2,Sergiu Shova3, Marius Andruh2, Cristian Silvestru1
1
Centre of Supramolecular Organic and Organometallic Chemistry, Faculty of Chemistry and
Chemical Engineering, Babeș-Bolyai University, 11 Arany János Street,400028, Cluj-Napoca,
România
2
Inorganic Chemistry Laboratory, Faculty of Chemistry, University of Bucharest, Str. Dumbrava
Rosie nr. 23,020464, Bucharest, Romania
3
‘Petru Poni’ Institute of Macromolecular Chemistry, Aleea Grigore Ghica Vodă, 41A, 700487 Iași,
România
E-mail: asava@chem.ubbcluj.ro

Coordination polymers with high stability and porosity have long been pursued
fortheir gas storage properties in clean energy or as high-capacity adsorbers for separation
needs.1 In this work, we present a new and optimised synthesis for the rigid tetrahedral ligand2
[Sn(p-C6H4CO2)4]4− (L)and its use for the synthesis of six new coordination polymers with
Zn(II), Co(II) or Cd(II), all characterized by single-crystal X-ray diffraction
techniques.[Co(L)(CH3OH)4](CH3OH)2 (1) and[Zn2(L)(2-amp)3](H2O)4.75(2), [2-amp = 2-
(aminomethyl)pyridine]form mono-dimensional chains, [Zn2(L)(cyclam)2](H2O)2.2(3)(cyclam
= 1,4,8,11-tetraazacyclotetradecane) has a bi-dimensional wave structure,
while[Zn2(L)(CH3OH)3](CH3OH)1.25(H2O)1.25 (4), [Zn2(L)(DMF)2(H2O)](DMF)2(H2O) (5)
(Scheme 1) and [Cd2(L)(DMF)2(H2O)](DMF)2(H2O)2 (6) exhibit three-dimensional networks.

L–H4 (5)
Scheme 1. Synthesis of [Zn2(L)(DMF)2(H2O)](DMF)2(H2O) (5), which displays atwo-fold
interpenetrated adamantanoid network.
1. H-C. Zhou, J. R. Long, O. M. Yaghi, Chem. Rev. 112 (2012) 673-674.
2. M.Veith, A. Rammo, C. Kirsch, L. Khemtémourian, D. Agustin, Organometallics 689 (2004)1546-1552.

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TOWARDS A COMPREHENSIVE OVERVIEW OF E-O AND E-N CHEMICAL

BONDINGS (E = SI, GE, SN) IN NEUTRAL AND CATIONIC SPECIES; A DFT
CASE STUDY
Ionut-Tudor Moraru, Florin Teleanu, Gabriela Nemes
Facultatea de Chimie şi Inginerie Chimică, Universitatea Babeş-Bolyai,
11 Arany Janos Street, RO-400082 Cluj-Napoca, Romania
e-mail: mit@chem.ubbcluj.ro
The molecular structures of (H3E)2O and (H3E)3N species (E = Si, Ge, Sn) display
particular features, with Valance Bond Theory failing to predict their accurate geometries.
The E-O-E moieties (E =Si, Ge, Sn) within inorganic ethers exhibit an unusual bent, with
values of 150˚ for Si-O-Si and 130˚-140˚ for Ge-O-Ge and Sn-O-Sn.As for E3N inorganic
amines, their geometries are rather planar and not pyramidal as in their organic analogues.
Additionally, E-O and E-N chemical bonds are significantly shorter then the length obtained
by summing their covalent radii.
The nature of the Si-O bond was intensively investigatedby Computational Chemistry
methodsduring the last decades, as siloxanes represent the back-bone of silicon based
industry. Recent studies shed more light on its elusive character, addressing the structural
dilemma of siloxanes in terms of hyperconjugative effects.1,2 Similar patterns were
additionally developed for the Ge-O and Sn-O chemical bonds3. However, less theoretical
data is available for the cationic species of these inorganic ethers, while acomprehensive
investigation is demanded for the family of E3N derivatives.
The aim of this study is to gain insight on the structure and chemical bonding of
(R3E)3N inorganic amines, their hypervalent cationic species [(R3E)3NR’]+ and also for the
[(R3E)2OR’]+ cationic oxanes (E = Si, Ge, Sn; R = H, Me; R’ = H, EH3). For all these
purposes, DFT calculations were performed. Natural Bond Orbital (NBO) techniques were
carried out on the optimized structures.

References:
1. F. Weinhold, R. West, Organometallics 30, 5815 (2011).
2. F. Weinhold, R. West, J. Am. Chem. Soc. 135, 5762, (2013).
3. I.-T. Moraru, P. M. Petrar, G. Nemes, J. Phys. Chem. A121, 2515 (2017).

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XXXV-th ROMANIAN CHEMISTRY CONFERENCE

COMPUŞI COORDINATIVI AI UNOR METALE TRANZIŢIONALE

CU ACIDUL 2,2'-DITIODIBENZOIC ÎN PREZENŢA PUNŢILOR BIPIRIDINICE

Aliona Vitiu1,2, Lilia Croitor1, Anatolii Siminel1, Eduard Coropceanu2,3, Polina Bouroş1,3
1
Institutul de Fizică Aplicată, Chişinău, R. Moldova
2
Institutul de Chimie, Chişinău, R. Moldova
3
Universitatea de Stat din Tiraspol, Chişinău, R. Moldova

Polimerii coordinativi (PC) reprezintă o clasă de materiale cu cea mai rapidă evoluţie. Interesul
faţă de acest tip de compuşi este generat de potenţialul remarcabil de utilizare al acestora în aşa
domenii cum sunt sorbţia gazelor şi/sau solvenţilor, separarea gazelor, senzori şi cataliză, în timp ce
pentru unii din ei au fost depistate proprietăţi optice neliniare sau magnetice. Un impuls pentru
cercetarea PC rămâne crearea materialelor poroase anorganice-organice asemănătoare zeoliţilor.
O caracteristică a PC care conţin liganzi cu fragmentul –S–S– este legată de transformările
variabile în funcţie de condiţiile de reacţie. Reacţia de difuzie lentă a acidului 2,2'-ditiodibenzoic
(H2dtdb) cu diverse metale tranziţionale în prezenţa unor liganzi N-donori conduce la formarea
diferitor PC, în care au fost depistate un şir de transformări anume cu ligandul H2dtdb, legate atât de
scindarea legăturii S–S, cât şi a legăturii C–S, iar uneori şi oxidarea unui atom de S1. Modificările
diversificate din acest ligand, cum ar fi scindarea oxidativă sau reductivă, extrudarea unui sulf sau
întroducerea unui atom suplimentar (S, C, N) pot duce la formarea compuşilor discreţi (0D) sau PC
cu dimensionalităţile 1D, 2D şi 3D. Ligandul H2dtdb şi liganzii bidentaţi N-donori din clasa
bipiridinelor au contribuit la formarea unei serii de compuşi cu sărurile de Mn(II), Co(II), Cu(II),
Zn(II) şi Cd(II), compoziţia şi structura cărora au fost determinate în baza metodelor fizico-chimice
contemporane (spectroscopia IR, difracţia razelor X pe monocristal etc.). În rezultatul determinării
structurii au fost stabiliţi zece compuşi coordinativi noi, dintre care un compus este monuclear, iar
restul – PC cu diverse dimensionalităţi. În cinci compuşi ligandul dtdb2- coordinează prin grupele
carboxilice manifestând diferite moduri de coordinare, în trei din ei s-a depistat scindarea legăturilor
S–S şi C–S cu formarea anionilor tiodibenzoic şi tiobenzoic, iar într-un caz – cu oxidarea ligandului
până la SO42-. O analiză a spectrelor de luminiscenţă ale acestor compuşi a evidenţiat, că
proprietăţile luminescente ale lor în mare parte depind de liganzii utilizaţi.
1. Gorobet A., Vitiu A., Petuhov O., Croitor L. Polyhedron. 2018, 151, 51–57.

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CHARGE TRANSFER AND POLARIZATION EFFECTS IN MgtE MAGNESIUM

CHANNELS REGULATE SELECTIVITY
Dragos Lucian Isaca, Andrei Neamtua,b*, Tudor Vasiliua, Cornel Cojocarua, Anton
Airineia, Mariana Pintealaa
a
“Petru Poni” Institute of Macromolecular Chemistry Iasi, Grigore Ghica Voda Al. No. 41A, Iasi, Romania
b*
Department of Physiology, “Gr. T. Popa” University of Medicine and Pharmacy of Iasi, Str.
Universitatii nr. 16, Iasi, Romania;corresponding e-mail: andrei.neamtu@umfiasi.ro

The Mg2+ and Ca2+ hydration cluster represents a vital contribution, especially in the transport of
ions and water1 and play a key role in many biological systems (e.g. metalloenzymes2). Magnesium
transporters are essential for life, participating in many vital processes, such as: enzymatic reactions,
transmembrane ion fluxes, co-factor in genomic replication machinery and calcium antagonism. MgtE
is a bacterial membrane channel highly selective for Mg2+ ions compared to other divalent cations like
Ca2+. However, even if MgtE channel has been extensively described structurally in both Mg2+ and
Ca2+ bound form, the mechanism of selectivity is still unclear. The study aimed to pinpoint how the
selectivity arises from a mechanistic perspective using QM, QM/MM and molecular dynamics (MD)
calculations. In this case the Ca2+ ion surrounded by n number of water molecules was linked to the
selectivity filter of the MgtE, which is located between two aspartate residues (ASP). The exact
number of water molecules ,n, is unknown and still represents a matter of debate for experimentalists.
Using QM results,a new model for MD computation3 was chosen to establish the solvation shell of
Ca2+ ion, because the classical force fields used in MD intrinsically neglect non-trivial electronic
effects. The results from the new MD (~500 ns) calculations included the polarization parameters and
were in line with the QM/MM model. The established number of water molecules in this study was
equal to n=7. Also, the presented results were in agreement with the experimental data. Hence, the
charge transfer and polarization effects played a key role in the formation of the Ca2+ hydration cluster
and elegantly explain the selectivity of the MgtE channel.
Acknowledgements: This work was supported by a grant ofthe European Union’s Horizon
2020 research and innovation programme under grant agreement no. 667387
WIDESPREAD2-2014 SupraChem Lab.
1. E. Bruzzi, A. J. Stace, R Soc Open Sci. 2017, 4, 160671.; 2. S. E. Rodriguez-Cruz, R. A. Jockusch,E. R.
Williams, J Am Chem Soc. 1998, 120, 5842;3. J. Yoo, J. Wilson, A. Aksimentiev,Biopolymers. 2016, 105, 752.

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STRUCTURAL INFLUENCE OF DIFFERENT COUNTER IONS IN COPPER(II)

COMPLEXES WITH HEXADENTATE SCHIFF BASE AS LIGAND
Ildiko Buta1, Anamaria Ardelean1, Carmen Cretu1, Peter Lönnecke2, Evamarie Hey-
Hawkins2, Marius Andruh3, Otilia Costisor1
1
Institute of Chemistry of the Romanian Academy, 24 Mihai Viteazu Bvd. 300223-Timisoara, Romania
2
Leipzig University, Faculty of Chemistry and Mineralogy, Institute of Inorganic Chemistry,
Johannisallee 29, 04103-Leipzig, Germany
3
University of Bucharest, Faculty of Chemistry, Inorganic Chemistry Laboratory, 23 Dumbrava Rosie
Str. 020464-Bucharest, Romania

Schiff base complexes of copper(II) continue to generate interest due to their potential
applications in fields as photo-catalysis1 and magnetic materials2.
Here, we report the influence of counter-ions on the coordination mode of the
deprotonated N,N’-bis[(2-hydroxybenzylideneamino)-propyl]-piperazine (H2L) Schiff
baseligand (Figure 1) with copper(II) ion. Three copper(II) complexes [Cu2L(CH3COO)2]
(1),[Cu3L2(NO3)](NO3)·2MeOH·2H2O(2)and[Cu9L6(µ3-ClO4)2](ClO4)4∙4CHCl3(3)containing
differentanions, i.e.CH3COO-, NO3- andClO4-,were synthesized and structurally characterized.
The nature of the complexes has been established by elemental analysis, and structural
information was obtained by single crystal X-ray diffraction and FT-IR spectroscopy.

Figure 1. The molecular structure of H2L ligand

In complex 1,the ligand acts as a symmetrical binucleatig ligand through the two N2O donor
atom sets locatedon each side of the piperazine ring. Astrongly distorted square pyramidal
environment of copper is achieved by chelating acetate groups.Compounds2and 3 consist of a
trinuclear Cu3L22+moietyin which L2-coordinatesthe marginal copper(II) in an unsymmetrical
mode via anN3O donor atom set and the central copper ionvia the remaining NO donor atoms.
The marginal copper(II) ions are in a distorted square pyramidal environment, whereas the
central one shows a distorted square planar (τ4 = 0.355 and τ4’ = 0.365) (2) andsquare planar (τ4
= 0) (3) geometry, respectively.In 2,the trinuclear units are linked by nitrato ligands forming a
1D chain, whereas in 3, the µ3-bridging mode of perchlorato ligand affords the formation of a 2D
network.

References
[1] M. Dostani, A. H. Kianfar, M. M. Momeni, J. Mater. Sci.: Mater.Electron.2017, 28, 633-640.
[2] S. Thakurta, P. Roy, R. J. Butcher, M. S. El Fallah, J. Tercero, E. Garribba, S. Mitra, Eur. J. Inorg. Chem.
2009, 4385-4395.
Acknowledgements
The authors acknowledge the support of the Romanian Academy, Project 4.1.

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ROLE OF SIROHEME AND THE FE4S4 CLUSTER IN THE ACTIVE SITE OF SULFITE
REDUCTASE
Adrian Brânzanic1, Ulf Ryde,2, Radu Silaghi-Dumitrescu1
1
Department of Chemistry, Babes-Bolyai University, Cluj-Napoca , Romania
2
Department of Theoretical Chemistry, Lund University, Lund, Sweden
The active site of sulfite reductase (SiR) consists of an unusual siroheme–Fe4S4 assembly (where
the siroheme is connected to the iron–sulfur cluster via a cysteinate sulfur) and serves for multi-electron
redox reactions. The electronic details of the siroheme–cluster interactions have not been explored so far
to a major extent. Density functional calculations (DFT) have previously been reported on the catalytic
cycle of SiR mostly using a simple iron-porphyrin model, without accounting directly for the role of the
iron–sulfur cluster and with little attention to the importance of the special variant of heme employed in
SiR. Reported here is the first extensive DFT investigation into the structural interplay (in terms of
geometry, molecular orbitals and magnetic interactions) between the siroheme and the Fe 4S4 center as
well as on the importance of the covalent modifications within siroheme compared to the more common
hemeb. In order to discern between effects of the charge vs magnetic interactions, also we also
examined a model where the Fe4S4 cluster is replaced by zinc. Given the importance of spin states in
interactions observed in SiR, the choice of the functional employed in the DFT calculations may be
essential; therefore, a calibration is performed using a set of four problematic cases of bioinorganic Fe
heme and non-heme centers. Out of 11 functionals tested, B97-D, M06-L and B3LYP offer the best
performance – although none of them correctly predict the spin state in all test cases. The latter two
functionals were employed for exploring a wide range of SiRmodels. Relative energies of spin states,
redox potentials, energy decomposition (electrostatic, exchange-repulsion, orbital relaxation, correlation
and dispersion interactions) and Mayer bond indices are examined in this respect. The cubane cofactor is
found to influence the siroheme system by decreasing the absolute value of its redox potential and by
stabilizing the siroheme–cysteine bond interaction. The siroheme removes the quasi-degeneracy
between the intermediate and high-spin states found in ferrous systems by preserving the latter as
ground state. Furthermore, a molecular orbital analysis suggests that siroheme would indeed be more
adept than heme in terms of charge transfer to/from a cubane FeS cluster. The higher-spin preference
and the increased accessibility of multiple spin states are likely to be important in selective binding of
the substrate and of the subsequent reaction intermediate, and in efficient changes in redox states
throughout the catalytic cycle.

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METAL COMPLEXES AS R2 RIBONUCLEOTIDE REDUCTASE INHIBITORS:

ELUCIDATION OF STRUCTURE-ACTIVITY RELATIONSHIP

Mirela-Fernanda Zaltariov
‘‘Petru Poni’’ Institute of Macromolecular Chemistry, Aleea Grigore Ghica Voda 41A, Iasi
700487, Romania

In this work we aimed to elucidate the structure-activity relationship (SAR) and to

disclose the potential as R2 RNR inhibitors of new six proligands and six dicopper(II)
complexes. The compounds were fully characterized by spectroscopic techniques (IR, UV-vis,
ESI-MS and NMR), analytical and X-ray diffraction analysis. Their antiproliferative activity was
examined in several human cancer and one noncancerous cell lines.
Several of the compounds showed high cytotoxicity andmarked selectivity for cancer
cells. One lead dicopper(II) complex and one proligand were found to be able to bind to the
protein with binding affinities in the low micromolar range, as well as having a noticeable effect
on the R2 tyrosyl radical (Y·) species (Figure 1).

Figure 1. Predicted hydrogen-bonding interaction between a dicopper(II) complex and Ser264 in

R2. An alteration to Ser264 conformation may lead to further conformational changes and
modulate protein activity.

Acknowledgements:This work was supported by a grant of Ministery of Research and

Innovation, CNCS - UEFISCDI, project number PN-III-P1-1.1-PD-2016-1027 (Contract
5/2018), within PNCDI III.

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DETAILED CHARACTERIZATION OF HEAVY AND LIGHT CRUDE OIL

ASPHALTENES BY EXPERIMENTAL AND SIMULATION APPROACHES
Salim Ok1,*, Navvamani Rajasekaran1,Muhammad Sabti1, Raffaela Cabriolu2,Mehdi
Mahmoodinia2. Anders Lervik2, Titus van Erp2
1
Petroleum Research Center, Kuwait Institute for Scientific Research, P.O. box 24885 Safat,
13109, Kuwait
2
Department of Chemistry, Norwegian University of Science and Technology (NTNU)
Høgskoleringen 5, Realfagbygget D3-117, 7491 Trondheim, Norway

One of the major problems with heavy oil fractions is their complexity making the analysis
problematic. Among these structures, asphaltene is the most complex one. The exact structure
clarification remains uncertain besides several efforts. Therefore, clarification of the asphaltene
nature requires further efforts by combining both experimental and computational approaches.
Understanding the asphaltene chemical structure is a key for effective processing of crude oils, and
clarifying the asphaltene nature will help with designing crude oil upgrading processes. In the
current contribution, we combine spectroscopy techniques of attenuated total reflection Fourier
Transform Infrared ATR-FTIR, and Diffuse reflectance infrared Fourier transform (DRIFT)
techniques besides Raman spectroscopy and nuclear magnetic resonance (NMR) spectroscopy, and
molecular dynamics (MD) simulations. The asphaltenes in the present study are extracted from
crude oils of Kuwait, and Maya crude oil of Mexico. DRIFT and ATR-FTIR revealed indexing
information in addition to clarification of different functional groups of asphaltene samples.
Average molecular sizes of condensed polyaromatic cores of asphaltene samples are determined
from the integrated intensities of graphitic bands in the Raman spectra. NMR spectroscopy applied
in solutionhelped with the clarification of the chemical structures of asphaltene samples even down
to ‘bay’ and ‘fjord’ type structures. Based on the NMR correlations, various chemical structures
(polyaromatic cores with aliphatic chains, porphyrin derivatives, organic salts) are proposed.
Experimental results indicate a higher average molecular size and more complicated chemical
structure for the light crude oil asphaltenes than the heavy crude oil ones. Density and solubility
parameters of asphaltenesare also determined by simulations.

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NEW LIQUID-CRYSTALLINE PLATINUM(II) POLYCATENAR COMPLEXES FOR

POLARIZED LIGHT EMISSION

A. A. Andelescua, A. M. Spirache a, L. Cseh a, O. Costişor a,B. Donniob, and E. I. Szerb a

a
Institutul de Chimie Timișoara al Academiei Române, B-dul. Mihai Viteazu nr. 24, 300223-
Timișoara, România.
b
Institut de Physique et Chimie des Matériaux de Strasbourg, 23 Rue du Loess, Strasbourg,
67034, France

Polarized emission is relevant for several opto-electronic applications. The main drawback is that
the polarization of light is achieved with a polarizer incombination with a non-polarized light
source, which wastes 50% of the produced light by absorption.1 Luminescent liquid crystalshave
attracted interest in this area because of direct production of polarized light resulting in devices
with improved energy efficiency, which is technologically and economically important.1,2
In this respect, liquid crystals based on platinum(II) complexes are very attractive candidates for
the fabrication of integrative optical devices. They have the possibility of achieving high internal
quantum efficiencies of the polarization emission, whereas the square-planar geometry and
intermolecularPt…Pt interactions favor self-organized systems, orientated morphologies and high
mobility.3,4
Based on these features, we report herein the synthesis and characterization of new Pt(II) liquid
crystalline complexes, based on substitutedterpyridine ligands. The induction of room
temperature liquid crystalline properties was achieved by functionalization with several long
alkyl chains introduced in the molecular backbone of a Pt(II) precursor complexes. Their
mesomorphic properties were investigated by polarized optical microscopy and differential
scanning calorimetry. Preliminary results on the photophysical properties in solution and
condensed states will be presented.

[1]Y. Wang et al., J. Mater. Chem. C2015,3, 7993-8005.

[2]H. A. R. Pramanik et al.Chem. Eur. J.2013, 19, 13151 – 13159.
[3] Y. Wang et al., J. Phys. Chem. C2012, 116, 5908−5914.
[4] F. Camerel et al., Angew. Chem. Int. Ed. 2007, 46, 2659 –2662.

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COORDINATION POLYMERS OF VARIOUS TOPOLOGIES BUILT FROM

TETRADENTATE SPACERS

Teodora Mocanua, Sergiu Shovab, Cristian Silvestruc, Ion Grosuc, Marius Andruha

a
Inorganic Chemistry Laboratory, Faculty of Chemistry, University of Bucharest, Str. Dumbrava Rosie
nr. 23, 020464, Bucharest, Romania
b
“Petru Poni” Institute of Macromolecular Chemistry, Aleea Grigore Ghica Voda, 41A, 700487 Iasi,
Romania
c
Centre of Supramolecular Organic and Organometallic Chemistry, Department of Chemistry, Faculty of
Chemistry and Chemical Engineering, Babeş-Bolyai University, 11 Arany Janos, 400028, Cluj-Napoca,
Romania

Coordination polymers are of tremendous interest, especially due to the remarkable

properties they may develop, like porosity, high surface area, luminescence, magnetism.1 Crystal
engineering based on self-assembling directed by metal-ligand binding is focusing on tuning the
properties towards functional applications.
Rigid tetrahedral and tetragonal organic spacers have recently emerged as a structural-
generating feature in designing coordination systems with robust, highly connected topological
nets.2 Tetradentate tectons built around a tetrahedral centre (adamantane, C, Si, Ge) are expected
to generate 3-D solid state architectures based on the spatial orientation of the ligating groups.
The overall topology of the resulting framework is stongly influenced by the nature of the
assembling metal ions. The interaction of the metal nodes and the spirobifluorene derivatives
bearing donor groups generates structural motifs imprinted with the orthogonality of the fluorene
units’ arrangement within the ligand molecules.
Herein, we report the synthesis and structural characterization of several coordination
polymers constructed from tetratopic spacers (adamantane, tin or spirobifluorene derivatives)
and metal-based assembling species (square planar, tetrahedral or angular nodes).
References:
1. (a) M. L. Foo, R. Matsuda, S. Kitagawa, Chem. Mater., 2014, 26, 310, (b) S. Kitagawa, R. Kitaura, S. Noro,
Angew. Chem. Int. Ed., 2004, 43, 2334; (c) C. Janiak, Dalton Trans., 2003, 2781;
2. (a) T. Muller, S. Bräse, RSC Adv., 2014, 4, 6886; (b) P. K. Clews, R. E. Douthwaite, B M. Kariuki, T. Moore,
M. Taboada,. Cryst. Growth Des., 2006, 6, 1991; (c) F. Moreau, N. Audebrand, C. Poriel, V. Moizan-Baslé, J.
Ouvry, J. Mater. Chem., 2011, 21, 18715; (d) C. S. Collins, D. Sun, W. Liu, J. –L. Zuo, H.- C. Zhou, J. Mol.
Struct., 2008, 890 , 163.

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NEW ORGANOTIN(IV) COMPLEXES WITH VARIOUS DIMENSIONALITIES

Delia-Laura Popescu
University of Bucharest, Faculty of Chemistry, Inorganic Chemistry Department,
23 Dumbrava Roşie, 020464-Bucharest, Romania
Organotin(IV) coordination compounds have been the subject of interest for some time
due to their properties, structural aspects, and potential biomedical, environmental, and
commercial applications.1-4 A new series of coordination compounds with different organotin(IV)
subunits as nodes and organic bridging ligands as spacers were prepared. The combination of
organotin(IV) building blocks with O- and N-donor ligands resulted in the formation of new
extended structures with 0-D, 1-D, 2-D, and 3-D dimensionalities. The influence of the nature of
organotin(IV) nodes and the bridging ligands on dimensionality of the new systems obtained was
investigated. All the synthesized compounds have been characterized by elemental analysis,
standard spectroscopic techniques (FTIR, UV-Vis-NIR, NMR), thermal analysis, as well as by
single crystal and powder X-ray diffraction. The ligands, metal precursors and their corresponding
organotin(IV) complexes have also been screened for antimicrobial activities.

Figure 1. Structure of 1-D coordination polymer {(Ph3Sn)(µ-bpa)(Ph3Sn)(µ-tpa)}n.

Hydrogen atoms were omitted for clarity.
References:
[1]. Pellerito, L., Nagy, L., Coord. Chem. Rev., 2002, 224, 111-150;
[2] Basu Baul, T.S., Appl. Organometal. Chem., 2008, 22, 195-204;
[3] Ghionoiu, A.-E., Popescu, D.-L., Maxim, C., Madalan, A.M., Haiduc, I., Andruh, M., Inorg. Chem.
Commun., 2015, 58, 71-73;
[4] Iqbal, M., Ali, S., Haider, A., Khalid, N., Rev. Inorg. Chem., 2017, 37, 51-70.

Acknowledgments: Financial support for this work was provided by the Romanian Executive Agency for Higher
Education, Research, Development and Innovation (UEFISCDI) through the projects PN-II-RU-PD-2012-3-
0528 and PN-III-P4-ID-PCCF-2016-0088.

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XXXV-th ROMANIAN CHEMISTRY CONFERENCE

NOVEL DIPHOSPHASTANAPROPENES. TOWARDS NEW UNSATURATED

PHOSPHORUS CONTAINING DERIVATIVES.
Raluca Septelean , Gabriela Nemes

Faculty of Chemistry and Chemical Engineering, Babeş-Bolyai University

str. Arany Janos nr.11 , 400028, Cluj-Napoca, Romania
raluca.septelean@gmail.com

Organophosphorus chemistry is an important field of organometallic chemistry due to

the diversity and complexity as well as the large applicability of these compounds. Due to the
design of new bulky substituents as stabilizing units of the multiple bonds1, a great number of
unsaturated organophosphorus compounds could be obtained and characterized in the last
decades. Diphosphaalkenes (containing the P=P unit), phosphaalkenes (P=C) as well as fewer
and less stable cumulenic systems such as phosphaallenes (P=C=C)2 1,3-diphosphaallenes
(P=C=P)3 and heterophosphaallenes (P=C=E, E-heavier element for group 14 or 15) have
been described in the literature due to the advance of the synthetic methods.
A large variety of organophopshorus unsaturated compounds arises due to the large
valence and coordination possibilities of the phosphorus atoms. Our group focuses on the
study of 1,3-diphosphapropenes containing tri- or pentavalent phosphorus atoms which,
having multiple coordination centers, can be used as ligands to transition metals and therefore
be important molecular bricks for larger organometallic systems.
We describe here our advancement in the field of 1,3-diphosphapropenes: the
synthesis, characterization and their reactivity study, compounds of interest for the
development of the field of unsaturated phosphorus organometallic species.

References
1. M. Yoshifuji, J. Organomet. Chem., 2000, 611, 210.
2. M ,Yoshifuji, K. Toyota, K. Shibayama,N. Inamoto, Tetrahedron Lett., 1984, 25,1809.
3. F. Ramires, N. B. Desai, B. Hansen, N. McKelvie, J. Am. Chem. Soc., 1961, 83, 3539.

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SYNTHESIS, CHARACTERIZATION AND REACTIVITY STUDY OF SOME NEW

GERMAPHOSPHAALKENYL TYPE DERIVATIVES

Lavinia Buta, Gabriela Nemeș

Faculty of Chemistry and Chemical Engineering, Babeş-Bolyai University
str. Arany Janos nr. 11, 400028, Cluj-Napoca, Romania
lavinia.buta@yahoo.ro ; gabriela.nemes@ubbcluj.ro

The reaction between a freshly prepared phosphaalkenyllithium, Mes*PCCl(Li) 1, and

different equivalents of 9,9-dichloro-9-germafluorene conducted to the formation of new
germaphosphapropene type compounds. These newly obtained derivatives were completely
characterized in solution and solid state. Their stability in air/moisture environment was also
tested proving that these compounds were stable up to several weeks.
The reactivity of a new germaphosphapropene was tested in the presence of lithium
and butyllithium, showing different behaviour compared with the previously reported cases. 2
A new palladium complex of a germadiphosphapropene was also synthesized and
evidenced using multinuclear NMR spectroscopy methods. The complete characterization and
the study of its possible catalitic activity are still in progress.

References

1. R. Septelean, G. Nemes, J. Escudie´, I. Silaghi-Dumitrescu, H. Ranaivonjatovo, P. M. Petrar, H. Gornitzka,

L. Silaghi-Dumitrescu and N. Saffon, Eur. J. Inorg. Chem., 2009, 628.
2. (a) H. Ramdane, H. Ranaivonjatovo and J. Escudie, Organometallics, 1996, 15, 3070; (b) Y.E. Harouch, H.
Gornitzka, H. Ranaivonjatovo and J. Escudie, J. Organomet. Chem., 2002, 643-644, 202; (c) H.
Ranaivonjatovo and J. Escudie, Organometallics, 2007, 26, 1542; (d) J. Escudie and G. Nemes, Comptes
Rendus Chimie, 13 (8-9), 954; (e) D. Matioszek, T.-G. Kocsor, A. Castel, G. Nemes, J. Escudie, N. Saffon,
Chem. Commun., 2012, 48, 3629; (f) I. Pailhours, H. Ranaivonjatovo, J. Escudie, J.-P. Declercq and A.
Dubourg, Organometallics, 1999, 18, 1622; (g) G. Cretiu Nemes, H. Ranaivonjatovo, J. Escudie, I. Silaghi-
Dumitrescu, L. Silaghi-Dumitrescu and H. Gornitzka, Eur. J. Inorg. Chem., 2005, 1109.

CHIMIE ANORGANICĂ, BIOANORGANICĂ ŞI ANALITICĂ

INORGANIC, BIOINORGANIC AND ANALYTICAL CHEMISTRY Page 20
 A XXXV-a CONFERINŢĂ NAŢIONALĂ DE CHIMIE 2018
XXXV-th ROMANIAN CHEMISTRY CONFERENCE

HOMO- AND HETERO METALLIC COMPLEXES CONSTRUCTED FROM

HEXAFLUOROACETYLACETONATO AND SCHIFF BASE COMPLEXES AS
BUILDING-BLOCKS

Mihaela I. Mocanu1, Sergiu Shova2, Francesc Lloret3, Miguel Julve3 and Marius Andruh1
1
Inorganic Chemistry Department, Faculty of Chemistry, University of Bucharest, Dumbrava Rosie, No. 23, Bucharest,
Romania, mihaela.mocanu2010@yahoo.com
2
“Petru Poni” Institute of Macromolecular Chemistry, Alea Gr. Ghica Voda 41A, 700487 Iasi, Romania
3
University of Valencia, Instituto de Ciencia Molecular (ICMOL), Valencia, Spain

Polynuclear complexes containing identical or different paramagnetic centers are of major interest in
coordination chemistry because of their relevance in molecular magnetism1, luminescent materials 2,
catalysis3, and model bioinorganic chemistry4.
Eight new homo- and heterometallic complexes have been synthesized and crystallographically
characterized: [Cu2(saldmpn)2(μ-OCH3)2Cu2(hfac)2] (1), [Ni2(valaepy)2(hfac)2] (2), [Cu(saldmpn)Co(hfac)2]
(3), [Cu2(salpn)2(μ-OCH3)2Ni2(hfac)2] (4), [Cu(saldmpn)Zn(hfac)2] (5), [Ni2(valampy)2(hfac)2] (6),
[Cu2(salpn)2Mn2(hfac)2] (7), and [Cu2(salpn)2Zn2(hfac)2] (8) [H2saldmpn] is the Schiff-base resulting from
condensation of salicylaldehyde with 2,2-dimethyl-1,3-diaminopropane, Hvalaepy and Hvalampy results
from the reaction of o-vanillin with 2-(2-aminoethyl)pyridine) and 2-aminomethyl-pyridyne,
respectively].6The structure of 1 consists of a neutral tetranuclear species that can be viewed as resulting
from mutual coordination of one {(hfac)Cu(μ-OCH3)2(Cu(hfac)} and two {Cu(saldmpn)} modules.
Compound 2 is a binuclear complex that results from two {Ni(hfac)(valaepy)} moieties, the nickel(II) ions
being bridged by the two phenoxido oxygen atoms. The heterobinuclear complex 3 results from coordination
of the [Cu(saldmpn)] metalloligand to cobalt(II) from the {Co(hfac) 2} unit. The magnetic properties of 1–3
have been investigated in the temperature range 1.9 - 300 K. An overall ferromagnetic behavior is observed
for 1 and 2.leading to S = 2 ground state for each one. The intermolecular CuII-CoIIexchange interaction in
3was found to be antiferromagnetic.
3.5

3.2
3.0
c T / cm mol K
-1
c T / cm mol K
-1

2.8
3

2.5
3

2.4
M

2.0 0 2 4 6 8 10
T/K

1.5
0 100 200 300
T/K

Figure 1. The structure of complex 1. Figure 2. Temperature dependence of the χMT

product for 1.

1. O. Kahn, Adv. Inorg. Chem., 1995, 43, 179;

2. T.D. Pasatoiu, C. Tiseanu, A.M. Madalan, B. Jurca, C. Duhayon, J.P. Sutter, M. Andruh, Inorg. Chem., 2011,
50, 5879;
3. D.S. Nesterov, O.V. Nesterova, A.J.L. Pombeiro, Coord. Chem. Rev., 2018, 355, 199;
4. F. Gloaguen, T.B. Rauchfuss, Chem. Soc. Rev., 2009, 38, 100;
5. M. I. Mocanu, S. Shova, F. Lloret, M. Julve, M. Andruh,J. Coord. Chem.,2018, 71, 693.

CHIMIE ANORGANICĂ, BIOANORGANICĂ ŞI ANALITICĂ

INORGANIC, BIOINORGANIC AND ANALYTICAL CHEMISTRY Page 21