Coordination Assemblies of Metallacyclic, Prismatic and Tubular Molecular Architectures Based on the Non‐rigid Ligands

Chen, Chun‐Long; Zhang, Jianyong; Su, Cheng‐Yong

doi:10.1002/ejic.200700187

Cited by 117 publications

(67 citation statements)

References 123 publications

(103 reference statements)

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“…www.chemeurj.org states (only spin down centers indicated, using the notation of Figure 3): one S = 15/2, five S = 9/2 ([1], [2], [3], [4] and [5]) and ten S = 3/2 ([1, 2], [1,3], [1,4], [1,5], [2,3], [2,4], [2,5], [3,4], [3,5] and [4,5]). The values of the nine J i constants resulting from these calculations are given in Table 3 (see Figure 3 for notation).…”

Section: Full Papermentioning

confidence: 99%

“…Apart from having aesthetically pleasing architectures (e.g. squares, [1] rectangles, [2] or pentagons [3] ) polymetallic clusters display unique magnetic properties at the molecular level such as single-molecule magnet (SMM) behavior, [4,5] quantum tunneling of the magnetization, [6] or quantum interference. [7] Most of the reported SMMs of 3d ions are based on the metals Mn, Ni, and Fe.…”

Section: Introductionmentioning

confidence: 99%

“…Originally, only perfectly octaheAbstract: A high-spin Co II cluster with a rare pentagonal molecular structure and formula [Co 5 A C H T U N G T R E N N U N G (CO 3 ) 2 A C H T U N G T R E N N U N G (bpp) 5 ]ClO 4 (1; Hbpp is 2,6-bis(phenyliminomethyl)-4-methylphenolate) has been synthesized and characterized by single-crystal Xray diffraction. This topology arises from fusing five [Co 2 A C H T U N G T R E N N U N G (bpp)] moieties in a cyclic manner around two CO 3 2À central ligands, resulting in propeller-like configuration. The irregular coordination of the carbonate ions to the metal centers results in a combination of coordination numbers (CNs) of the Co II ions of five and six.…”

Section: Introductionmentioning

confidence: 99%

“…The Co À O distances to the phenoxide oxygen atoms range from 1.990 (7) (6) . Within the Co pentagon, the distances between adjacent metal centers are 3.148(2) to 3.310 (2) , and the second neighbor separations are in the range 5.165(2) to 5.252 (2) . The crystal packing in complex 1 does not feature any obvious hydrogen bonding or p-p stacking interaction network (see Figure S3 in the Supporting Information).…”

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Double‐CO₃²⁻ Centered [Co^II₅] Wheel and Modeling of Its Magnetic Properties

Sarkar

Aromı́

Cano

et al. 2010

Chemistry A European J

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A high-spin Co(II) cluster with a rare pentagonal molecular structure and formula [Co(5)(CO(3))(2)(bpp)(5)]ClO(4) (1; Hbpp is 2,6-bis(phenyliminomethyl)-4-methylphenolate) has been synthesized and characterized by single-crystal X-ray diffraction. This topology arises from fusing five [Co(2)(bpp)] moieties in a cyclic manner around two CO(3)(2-) central ligands, resulting in propeller-like configuration. The irregular coordination of the carbonate ions to the metal centers results in a combination of coordination numbers (CNs) of the Co(II) ions of five and six. The bulk magnetization of this complicated magnetically exchanged system has been modeled successfully by employing a matrix diagonalization technique. For this, the combination of S=3/2 ions (CN=5) with ions exhibiting strong spin-orbit coupling (CN=6) has been considered and a perturbative approach to handle the data in the whole studied range of temperatures (2-300 K) yielding parameters of g and D (for the five-coordinate Co(II) ions), of A, κ, λ, and Δ (for the metals with spin-orbit coupling) and of the exchange constants J. The agreement with results from DFT calculations, also presented here, is remarkable.

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Section: Full Papermentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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confidence: 99%

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Double‐CO₃²⁻ Centered [Co^II₅] Wheel and Modeling of Its Magnetic Properties

Sarkar

Aromı́

Cano

et al. 2010

Chemistry A European J

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“…Long linking ligands containing terminal pyridyl rings, however, were recently employed to produce intriguing polymers with various topologies. [16][17][18][19][20][21][22][23][24][25] We have continually prepared long dipyridyl-, di(furan)-, di(thiophene)-, and di(ether)-type linking ligands and their coordination polymers. [26][27][28][29][30][31][32][33][34][35][36][37] We very recently prepared ligand L3 and its Co, Zn, and Cd coordination polymers (Chart 1).…”

Section: Chartmentioning

confidence: 99%

Double-Bridged 1-D Chain Polymers of Zinc and Cadmium Constructed by a Flexible Dipyridyl-Type Linking Ligand: {[ML_1.5(NO₃)₂].(CH₃OH)}∞ {M = Zn or Cd; L = (3-py)-CH₂-NH-(CH₃)C₆H₃-C₆H₃(CH₃)-NH-CH₂-(3-py)}

2009

Bulletin of the Korean Chemical Society

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Coordination polymers, also known as metal-organic frameworks (MOFs) or metallosupramolecular networks, continuously gain much attention due to their remarkable properties such as catalysis, nonlinear optical activity, spin crossover, luminescence, long-range magnetism, adsorption-desorption, and gas storage. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] These polymers are generally constructed by exploiting intramolecular metal-ligand covalent bonds, frequently as well as intermolecular interactions such as van der Waals contacts, π-π stacking, hydrogen bonding, and cation-π bonding.Aromatic multi-carboxylates and dipyridyl derivatives are typically used as linking ligands for the preparation of coordination polymers. Long linking ligands containing terminal pyridyl rings, however, were recently employed to produce intriguing polymers with various topologies. [16][17][18][19][20][21][22][23][24][25] We have continually prepared long dipyridyl-, di(furan)-, di(thiophene)-, and di(ether)-type linking ligands and their coordination polymers. 26-37We very recently prepared ligand L3 and its Co, Zn, and Cd coordination polymers (Chart 1).36 Ligand L3 is a reduced form of L2, and coordination polymers based on ligand L3 have novel intriguing topologies, consistent with our expectation that free rotations about the Ar-NH, NH-CH2, and CH2-(4-py) bonds may be possible. In other words, our previous work demonstrated that reduced species of diimine ligands possess a greatly enhanced structural flexibility, which may create novel polymers that cannot be obtained from the original rigid diimine ligands. As an extension of that work, we decided to reduce ligand L1 and to prepare coordination polymers by employing the resulting reduced ligand. It is worth noting that ligand L1 is a structural isomer of ligand L2 due to the different nitrogen positions in the terminal pyridyl rings. We report herein the preparation of ligand L, (3-py)-CH2-NH-(CH3)C6H3-C6H3(CH3)-NH-CH2-(3-py), and structures of its zinc and cadmium coordination polymers. Experimental SectionAll solid chemicals were purified by recrystallization, and all solvents were distilled and stored over molecular sieves. H} NMR data were collected on a 500 MHz Varian Inova spectrometer at the Cooperative Center for Research Facilities (CCRF) in Sungkyunkwan University. Infrared (IR) samples were prepared as KBr pellets, and their spectra were obtained in the range 400∼4000 cm -1 on a Nicolet 320 FTIR spectrophotometer. Elemental analyses were performed with an EA1110 (CE instrument, Italy) at the Korea Basic Science Institute. Ligand L1 was prepared by the literature method. 28 Preparation of (3-py)-CH2-NH-(CH3)C6H3-C6H3(CH3)-NH-CH 2 -(3-py) (L).To compound L1 (7.0 g, 17.9 mmol) in ethanol (50 mL) was added sodium borohydride (6.78 g, 179 mmol) in small portions with stirring at room temperature. The resulting mixture was stirred for 12 h, and then filtered. The remaining orange solid was extracted with dichloromethane (100 mL), and washed with water (30 mL × 3). Th...

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Antisymbiotic Self‐Assembly and Dynamic Behavior of Metallamacrocycles with Allylic Corners

Angurell

Ferrer

Gutiérrez

et al. 2010

Chemistry A European J

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The design and synthesis of discrete supramolecular architectures by metal-ligand self-assembly is an area of current interest. [1][2][3][4][5][6][7][8][9][10][11] The application of the directional bonding approach has proved to be very versatile, allowing the synthesis of many molecular triangles, squares, rectangles, pentagons, hexagons, and cages. [12][13][14][15][16][17][18] Among them, homometallic molecular squares, formed by the reaction of cis-protected square planar complexes with linear symmetric ditopic ligands, have been the most widely studied. [19][20][21][22][23][24][25] The assembly of metallamacrocycles containing different metal corners and/or nonsymmetric ligands using this method presents additional difficulties due to the possible generation of a mixture of isomers that are difficult to separate. To overcome this, they are generally obtained through modular self-assembly methodology. This strategy requires the initial synthesis of mononuclear complexes with strong covalently bound ligands that have additional donor sites available for coordination to further acceptor building blocks. [26][27][28] Nevertheless, several molecular triangles and squares have been recently assembled following the directional bonding approach by using nonsymmetric linkers and identical metal corners. Interestingly, in some cases, unexpected self-selection of a single linkage isomer was observed. [29][30][31][32][33] To analyze the large quantity of metallamacrocycles reported to date, the following classification is proposed, according to the nature of the assembled units: 1) species containing identical metal corners and symmetric linkers; 2) species containing identical metal corners and nonsymmetric linkers; and 3) species containing different metal corners and nonsymmetric linkers.Herein, we report the use for the first time of the directional bonding approach for the synthesis of metallamacrocycles displaying two different metal corners connected by a nonsymmetric ditopic linker. By the correct choice of the different units, that is, metal corners and ambidentate ligand, we have been able to promote its self-assembly producing molecular square architectures and, more interestingly, achieving the self-selection of a single linkage isomer.Evidently, the correct choice of a heteroditopic ligand in which the different (stereo)electronic characteristics of the donor groups could control the reactivity at the metal site is decisive. Thus, we focused our attention on the 4-PPh 2 py ligand (py = pyridine), given its hard-soft character. [34,35] Furthermore, the electronic nature of the ancillary ligands in the metal corners on the proposed assembly is also crucial for the self-selection process. As a result, complex [Pd(h 3 -2-Me-C 3 H 4 )A C H T U N G T R E N N U N G (cod)]A C H T U N G T R E N N U N G (CF 3 SO 3 ) was chosen as the source of {Pd(h 3 -2-Me-C 3 H 4 )} + , a potential metal corner that could provide a varied reactivity to the system, as expected for the allyl palladium species. On the other hand, the ...

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Coordination Assemblies of Metallacyclic, Prismatic and Tubular Molecular Architectures Based on the Non‐rigid Ligands

Abstract: This microreview covers recent advances in the assembly of coordination molecular architectures showing cyclic, prismatic and tubular structures based on the semi-rigid or flexible ligands. Four assembly routes are outlined depending on [a]

Cited by 117 publications

References 123 publications

Double‐CO₃²⁻ Centered [Co^II₅] Wheel and Modeling of Its Magnetic Properties

Double‐CO₃²⁻ Centered [Co^II₅] Wheel and Modeling of Its Magnetic Properties

Double-Bridged 1-D Chain Polymers of Zinc and Cadmium Constructed by a Flexible Dipyridyl-Type Linking Ligand: {[ML_1.5(NO₃)₂].(CH₃OH)}∞ {M = Zn or Cd; L = (3-py)-CH₂-NH-(CH₃)C₆H₃-C₆H₃(CH₃)-NH-CH₂-(3-py)}

Antisymbiotic Self‐Assembly and Dynamic Behavior of Metallamacrocycles with Allylic Corners

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Coordination Assemblies of Metallacyclic, Prismatic and Tubular Molecular Architectures Based on the Non‐rigid Ligands

Abstract: This microreview covers recent advances in the assembly of coordination molecular architectures showing cyclic, prismatic and tubular structures based on the semi-rigid or flexible ligands. Four assembly routes are outlined depending on [a]

Cited by 117 publications

References 123 publications

Double‐CO32− Centered [CoII5] Wheel and Modeling of Its Magnetic Properties

Double‐CO32− Centered [CoII5] Wheel and Modeling of Its Magnetic Properties

Double-Bridged 1-D Chain Polymers of Zinc and Cadmium Constructed by a Flexible Dipyridyl-Type Linking Ligand: {[ML1.5(NO3)2].(CH3OH)}∞ {M = Zn or Cd; L = (3-py)-CH2-NH-(CH3)C6H3-C6H3(CH3)-NH-CH2-(3-py)}

Antisymbiotic Self‐Assembly and Dynamic Behavior of Metallamacrocycles with Allylic Corners

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Double‐CO₃²⁻ Centered [Co^II₅] Wheel and Modeling of Its Magnetic Properties

Double‐CO₃²⁻ Centered [Co^II₅] Wheel and Modeling of Its Magnetic Properties

Double-Bridged 1-D Chain Polymers of Zinc and Cadmium Constructed by a Flexible Dipyridyl-Type Linking Ligand: {[ML_1.5(NO₃)₂].(CH₃OH)}∞ {M = Zn or Cd; L = (3-py)-CH₂-NH-(CH₃)C₆H₃-C₆H₃(CH₃)-NH-CH₂-(3-py)}