ORGANOMETALLIC COMPOUNDS AS BUILDING BLOCKS FOR

SUPRAMOLECULAR ARCHITECTURES

Cristian SILVESTRU

UNIVERSITATEA BABES-BOLYAI CLUJ-NAPOCA

“Diaspora în Cercetarea Ştiinţifică şi Învăţământul Superior din România

- Diaspora şi prietenii săi”

Timişoara, April 26-27, 2016

SUPRAMOLECULAR ARCHITECTURE

• The modern concept of Supramolecular Chemistry was introduced in 1978

by Jean-Marie LEHN, who won the Nobel Prize for his work in the area in

1987, in the words: "Just as there is a field of molecular chemistry based on

the covalent bond, there is a field of supramolecular chemistry, the chemistry

of molecular assemblies and of the intermolecular bond."

Building block - well-studied structural and functional units used to

build up larger functional architectures.

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Tecton - molecules which play the role of building blocks in a self-

assembled, ordered supramolecular structure.1,2 A tecton is defined as “any

molecule whose interactions are dominated by particular associative forces

that induce self-asssembly of an organized network with specific

architectural or functional features”.2

1. M. C. T. Fyfe, J. F. Stoddart, Acc. Chem. Res., 1997, 30, 393.

2. S. Simard, D. Su, J. D. Wuest, J. Am. Chem. Soc., 1991, 113, 4696.

SUPRAMOLECULAR ARCHITECTURE

• Metallo-supramolecular Chemistry is a term used to describe metal-

mediated self-assembly.

• the metal ions are used as templates in the organization of the molecular

building blocks and are thus chosen for their coordination numbers and

stereochemical preferences.

• the ligands are carefully designed for the formation of the synthetic target

i.e. with the appropriate use of spacer groups and the correct number and

spatial arrangement of the donor sites.

• Metal-directed self-assembly plays a key role in supramolecular chemistry

and has led to the development of an array of highly sophisticated

architectures including boxes, helicates, triangles, grids, etc.

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Building blocks

dative bonds

Supramolecular

architectures

ionic bonds

hydrogen bonding

C-H···π bonding

others

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STRATEGIES

Building blocks

• complex cation + anionic metalloligand

• complex cation + neutral metalloligand

• neutral complex + neutral metalloligand

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ORGANOMETALLIC COMPOUND

Mδ+—Cδ-

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ORGANOMETALLIC COMPOUND

Mδ+—Cδ-

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ORGANOMETALLIC COMPOUND

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4,4ʹ-Bipy as spacer

S. C. James, N. C. Norman, A. G. Orpen, J. Starbuck, CrystEngComm, 2000, 2, 67.

Cl(1)-Bi(1)-Cl(2) 177.0(2)o N(1)-Bi(1)-N(1a) 173.0(3)o

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Di(4-pyridyl)mercury(II) as tecton

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[Cu(Hmea)2(py2Hg)](ClO4)2·2py2Hg

(Hmea = monoethanolamine)

1D chain heterobimetallic coordination polymer [Cu(II)/Hg(II)]

T. Mocanu, C. I. Raţ, C. Maxim, S. Shova, V. Tudor, C. Silvestru, M. Andruh,

CrystEngComm, 2015, 17, 5474. 11

[Cu(Hmea)2(py2Hg)](ClO4)2·2py2Hg

• supramolecular layers resulting from Hg∙∙∙π and N–H∙∙∙N(py) interactions

• 3D supramolecular architecture through Hg∙∙∙O contacts established by

bridging perchlorato ions

T. Mocanu, C. I. Raţ, C. Maxim, S. Shova, V. Tudor, C. Silvestru, M. Andruh,

CrystEngComm, 2015, 17, 5474. 12

• 1D supramolecular double chain of the heterobimetallic coordination

polymers [Cu(II)/Hg(II)] through Hg∙∙∙π interactions

T. Mocanu, C. I. Raţ, C. Maxim, S. Shova, V. Tudor, C. Silvestru, M. Andruh,

CrystEngComm, 2015, 17, 5474. 13

[Cu2(pa)2(py2Hg)(ClO4)2]·0.5py2Hg·H2O

(Hpa = propanolamine)

• a 3D supramolecular architecture is built through N–H∙∙∙O(water) and

Hg∙∙∙O(perchlorate) interactions

T. Mocanu, C. I. Raţ, C. Maxim, S. Shova, V. Tudor, C. Silvestru, M. Andruh,

CrystEngComm, 2015, 17, 5474. 14

[Cu2(pa)2(py2Hg)2](BF4)2

(Hpa = propanolamine)

Detail of the 3D heterobimetallic coordination polymer [Cu(II)/Hg(II)]

T. Mocanu, C. I. Raţ, C. Maxim, S. Shova, V. Tudor, C. Silvestru, M. Andruh,

CrystEngComm, 2015, 17, 5474. 15

[Cu2(pa)2(py2Hg)2](BF4)2

3D heterobimetallic coordination polymer [Cu(II)/Hg(II)]

1D chain heterobimetallic coordination polymer [Ni(II)/Hg(II)]

L. Kiss, C. I. Raţ, C. Silvestru, unpublished results.

[Ni{S2P(OiPr)2}2(py2Hg)2]

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1D double chain heterobimetallic coordination polymer [Mn(II)/Hg(II)]

I. Grosu, C. I. Raţ, M. Andruh, C. Silvestru, unpublished results.

Tectons - Di(4-pyridyl)mercury(II)

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Organotin(IV) species – potential spacers

(SCN)SnMe2[C6H4(CH=NCH2CH2N=CH)C6H4]Me2Sn(NCS)

A. Somesan, R. A. Varga, C. Silvestru, unpublished results. 18

Organoantimony(III) species – potential spacers

A. Toma, C. I. Raţ, A. Silvestru, T. Rüffer, H. Lang, M. Mehring, J. Organomet. Chem., 2013, 745-746, 71.

[2-(Me2NCH2)C6H4]Sb(NCS)2

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C. Coza, A. Stegărescu, R. Şuteu, A. Silvestru, J. Organomet. Chem., 2015, 777, 71.

[2-(Me2NCH2)C6H4](Bu)Sn(NCS)2 [2-(Me2NCH2)C6H4]2Sn(NCSe)2

Organotin(IV) species – potential spacers

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Organoantimony(III) species as ligand

D. Copolovici, F. Isaia, H. J. Breunig, C. I. Raț, C. Silvestru, RSC Advances, 2014, 4, 26569.

[{2-(Me2NCH2)C6H4}Mes2SbPdCl2]

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Organotin(IV) compounds as tectons

I. Barbul, R. A. Varga, C. Silvestru, Eur. J. Inorg. Chem., 2013, 3146.

[2-(R-N=CH)C6H4]4Sn

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[2-(RN=CH)C6H4]4Sn

I. Barbul, R. A. Varga, C. Silvestru, Eur. J. Inorg. Chem., 2013, 3146. 50

[2-(O=CH)C6H4]4Sn

[2-(Me2NCH2CH2N=CH)C6H4]4Sn

Organotin(IV) compounds as tectons

Organotin(IV) compounds as tectons

[2-(R-N=CH)C6H4]4Sn

I. Barbul, R. A. Varga, C. Silvestru, Eur. J. Inorg. Chem., 2013, 3146. 23

Structural diversity of coordination cores in new homoleptic

tetraaryltin(IV) dioxolane, aldehyde and imines. First

octacoordinated double helicate tetraorganotin(IV) compound,

Eur. J. Inorg. Chem., 2013, 3146-3154.

DOI: 10.1002/ejic.201300245

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Organotin(IV) compounds as tectons

[Cl2Pd{2-(2′-PyCH2N=CH)C6H4}2SnCl2]

I. Barbul, R. A. Varga, K. Molloy, C. Silvestru, Dalton Trans., 2013, 42, 15427.

Dalton Transactions HOT Articles for September

(http://blogs.rsc.org/dt/2013/10/02/hot-articles-for-september/).

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Organoantimony(III) species as tecton

I. Chircă, C. Silvestru, unpublished results.

[2-(2′-PyCH2N=CH)C6H4]3Sb

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Organophosphorus(V) species as tecton

(n-Py)3P=E (n = 3, 4; E = O, S, Se)

26 L. Dubován, A. Pöllnitz, C. Silvestru, Eur. J. Inorg. Chem., 2016, 1521.

Organophosphorus(V) species as tecton

(n-Py)3P=E (n = 3, 4; E = O, S, Se)

26 L. Dubován, A. Pöllnitz, C. Silvestru, Eur. J. Inorg. Chem., 2016, 1521.

Organobismuth(III) species as tectons

A. Ben Kiran, A. Pollnitz, , S. Shova, M. Andruh C. Silvestru, unpublished results.

Ph3Bi[O(O)CC6H4N-4]2

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Organobismuth(III) species as tectons

A. Ben Kiran, A. Pollnitz, C. Silvestru, unpublished results.

[2,6-{O(CH2CH2)2NCH2}2C6H]BiCl2

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G. Strîmb, A. Pöllnitz, C. I. Raţ and C. Silvestru,

Dalton Trans., 2015, 44, 9927-9942.

[2,6-{MeN(CH2CH2)2NCH2}2C6H3]2Bi2O2·4H2O

Organobismuth(III) species as tectons

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Organotin(IV) compounds as tectons

R. A. Varga, C. Silvestru, unpublished results.

[{2-(Me2NCH2)C6H4}2Sn]3(PO4)2 [{2-(Me2NCH2)C6H4}2Sn]3(PO4)2(CuI)2

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Supramolecular Organic and Organometallic Chemistry Center

– SOOMCC –

Organometallic Chemistry Group

2013

http://www.chem.ubbcluj.ro/~ccsoom/organometallic/

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Supramolecular Organic and Organometallic Chemistry Center

– SOOMCC –

Organometallic Chemistry Group

http://www.chem.ubbcluj.ro/~ccsoom/organometallic/

Prof. Cristian SILVESTRU

Prof. Anca SILVESTRU

Lect. Dr. Richard VARGA

CSIII Dr. Ciprian RAŢ

CSIII Dr. Alpar PÖLLNITZ

CSIII Dr. Alexandra POP

CSIII Dr. Ana Maria PREDA

Dr. Ioana BARBUL

PhD students

Gabriela STRÎMB Ion CHIRCĂ

Ana Maria TOMA Marian OLARU

Ancuţa CÎRCU KISS Levente

Ahmad BEN KIRAN

MSc students

Adrian SOMEŞAN

Cristina COZA

Răzvan ŞUTEU

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GERMANY

Prof. Dr. Hans J. BREUNIG

Universität Bremen

Fachbereich 02: Biologie / Chemie

http://www.uni-bremen.de/

ROMANIA

Prof. Dr. Marius ANDRUH

Universitatea din Bucureşti

Facultatea de Chimie

http://www.unibuc.ro/

Collaborations

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• Ministerul Educatiei si Cercetarii

• National University Research Council

Financial support

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Why ?

Asked, in 1924,

“Why ?",

George Leigh Mallory, the first great alpinist decided to climb on the top of

Everest, gave a famous answer:

“Because it exist !".

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