Thiodiacetate-Manganese Chemistry with N ligands: Unique Control of the Supramolecular Arrangement over the Metal Coordination Mode

被引：22

作者：

Grirrane, Abdessamad ^{[1
]}

Pastor, Antonio ^{[1
]}

Galindo, Agustin ^{[1
]}

Alvarez, Eleuterio ^{[2
]}

Mealli, Carlo ^{[3
]}

Ienco, Andrea ^{[3
]}

Orlandini, Annabella ^{[3
]}

Rosa, Patrick ^{[4
,5
]}

Caneschi, Andrea ^{[4
,5
]}

Barra, Anne-Laure ^{[6
]}

Fernandez Sanz, Javier ^{[7
]}

机构：

[1] Univ Seville, Dept Quim Inorgan, Seville 41071, Spain

[2] Univ Seville, CSIC, Inst Invest Quim, Seville 41092, Spain

[3] CNR, Ist Chim Composti Organometall, I-50019 Florence, Italy

[4] Univ Florence, Dipartimento Chim, I-50019 Sesto Fiorentino, Italy

[5] Univ Florence, CNR INSTM RU Firenze, I-50019 Sesto Fiorentino, Italy

[6] UJF, Lab Natl Champs Magnet Intenses, CNRS, F-38042 Grenoble 9, France

[7] Univ Seville, Dept Quim Fis, E-41071 Seville, Spain

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2011年 / 17卷 / 38期

关键词：

manganese; metal-organic frameworks; noncovalent interactions; stacking interactions; thiodiac; BULK MAGNETIC-PROPERTIES; RAY CRYSTAL-STRUCTURES; MN-II COMPLEXES; PI-PI STACKING; Q-BAND EPR; MOLECULAR-STRUCTURE; ORGANIC FRAMEWORK; OXYDIACETATE COMPLEXES; STRUCTURAL DIVERSITY; HYDROGEN STORAGE;

D O I：

10.1002/chem.201100988

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Compounds based on the Mn-tda unit (tda=S(CH2COO)(2)(-2)) and N co-ligands have been analyzed in terms of structural, spectroscopic, magnetic properties and DFT calculations. The precursors [Mn(tda)(H2O)](n) (1) and [Mn(tda)(H2O)(3)]center dot H2O (2) have been characterized by powder and Xray diffraction, respectively. Their derivatives with bipyridyl-type ligands have formulas [Mn(tda)(bipy)](n) (3), [{Mn(N-N)}(2)(mu-H2O)(mu-tda)(2)](n) (N-N=4,4'-Me(2)bipy (4), 5,5'-Me(2)bipy, (5)) and [Mn(tda){(MeO)(2)bipy}center dot 2H(2)O](n) (6). Depending on the presence/position of substituents at bipy, the supramolecular arrangement can affect the metal coordination type. While all the complexes consist of 1D coordination polymers, only 3 has a copper-acetate core with local trigonal prismatic metal coordination. The presence of substituents in 46, together with water co-ligands, reduces the supramolecular interactions and typical octahedral Mn-II ions are observed. The unicity of 3 is also supported by magnetic studies and by DFT calculations, which confirm that the unusual Mn coordination is a consequence of extended noncovalent interactions (pi-pi stacking) between bipy ligands. Moreover, 3 is an example of broken paradigm for supramolecular chemistry. In fact, the desired stereo-chemical properties are achieved by using rigid metal building blocks, whereas in 3 the accumulation of weak noncovalent interactions controls the metal geometry. Other N co-ligands have also been reacted with 1 to give the compounds [Mn(tda)(phen)](2)center dot 6H(2)O (7) (phen=1,10-phenanthroline), [Mn(tda)(terpy)](n) (8) (terpy=2,2':6,2 ''-terpyridine), [Mn(tda)(pyterpy)](n) (9) (pyterpy=4'-(4-pyridyl)-2,2':6,2 ''-terpyridine), [Mn(tda)(tpt)(H2O)]center dot 2H(2)O (10) and [Mn(tda)(tpt)(H2O)](2)center dot 2H(2)O (11) (tpt=2,4,6-tris(2-pyridyl)-1,3,5-triazine). Their identified mono-, bi- or polynuclear structures clearly indicate that hydrogen bonding is variously competitive with pi-pi stacking.

引用

页码：10600 / 10617

页数：18

共 26 条

[21] CHEMISTRY OF 3D-METAL COORDINATION-COMPOUNDS WITH LIGANDS BASED ON THIO AND SELENIUM ANALOGS OF ORTHO-HYDROXYBENZALDEHYDES - COPPER(II) CHELATES WITH S-METHYL-N-1,N-4-DI-(THIOSALICYLIDENE)ISOTHIOSEMICARBAZIDE
GARNOVSKII, AD
GERBELEU, NV
KOCHIN, SG
MINKINA, LS
VASILCHENKO, IS
ARION, VB
INDRICHAN, KM
KOORDINATSIONNAYA KHIMIYA, 1989, 15 (10): : 1330 - 1333
[22] Syntheses, Structures, and Coordination Chemistry of Phosphole-Containing Hybrid Calixphyrins: Promising Macrocyclic P,N2,X-Mixed Donor Ligands for Designing Reactive Transition Metal Complexes (vol 130, pg 990, 2008)
Matano, Yoshihiro
Miyajima, Tooru
Ochi, Noriaki
Nakabuchi, Takashi
Shiro, Motoo
Nakao, Yoshihide
Sakaki, Shigeyoshi
Imahori, Hiroshi
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (39) : 14123 - 14123
[23] TRANSITION-METAL CHEMISTRY OF S,N-CONTAINING LIGANDS .2. MANGANESE(III), IRON(II), IRON(III), COBALT(III), NICKEL(II) AND COPPER(II) COMPLEXES WITH S-METHYL-N-(2-QUINOLYL)METHYLENDITHIOCARBAZATE AND S-METHYL-N-(1-ISOQUINOLYL)METHYLENDITHIOCARBAZATE
MOHAN, M
KUMAR, M
SYNTHESIS AND REACTIVITY IN INORGANIC AND METAL-ORGANIC CHEMISTRY, 1984, 14 (05): : 615 - 635
[24] STEREOCHEMICAL AND CONFORMATIONAL CONTROL OF METAL REDOX PROCESSES - THE COORDINATION CHEMISTRY OF THE MIXED N-DONOR AND S-DONOR MACROCYCLIC CROWNS [18]ANEN2S4 AND ME2[18]ANEN2S4
REID, G
SCHRODER, M
CHEMICAL SOCIETY REVIEWS, 1990, 19 (03) : 239 - 269
[25] TRANSITION-METAL COMPLEXES WITH SULFUR LIGANDS .108. A FACILE SYNTHESIS OF THE TERTIARY AMINE-THIOLATO LIGAND 'S(2)N(2)ME(2)'(2-) - INFLUENCE OF THE AMINOMETHYLATION ON THE COORDINATION CHEMISTRY OF NICKEL AND RUTHENIUM COMPLEXES WITH [M('S(2)N(2)R(2)')] FRAMEWORKS (R=H, CH3) - ('S(2)N(2)ME(2)'(2-)=1,2-ETHANEDIAMINO-N,N'-DIMETHYL-N,N'-BIS(2-BENZENETHILATO)(2-))
SELLMANN, D
RUF, R
KNOCH, F
MOLL, M
ZEITSCHRIFT FUR NATURFORSCHUNG SECTION B-A JOURNAL OF CHEMICAL SCIENCES, 1995, 50 (05): : 791 - 801
[26] Neutral coordination polymers based on a metal-mono(dithiolene) complex: synthesis, crystal structure and supramolecular chemistry of [Zn(dmit)(4,4′-bpy)]n, [Zn(dmit)(4,4′-bpe)]n and [Zn(dmit)(bix)]n (4,4′-bpy=4,4′-bipyridine, 4,4′-bpe = trans-1,2-bis(4-pyridyl)ethene, bix=1,4-bis(imidazole-1-ylmethyl)-benzene
Madhu, Vedichi
Das, Samar K.
DALTON TRANSACTIONS, 2011, 40 (48) : 12901 - 12908

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