Novel Metal-Organic Frameworks Incorporating [Cp degrees 2Mo2P4S] (Cp degrees=1-tBu-3,4-Me2C5H2), P4S3 and Cu2I2 Building Blocks

Groeger, Christian and Kalbitzer, Hans Robert and Pronold, Michael and Piryazev, Dmitry and Scheer, Manfred and Wachter, Joachim and Virovets, Alexander and Zabel, Manfred (2011) Novel Metal-Organic Frameworks Incorporating [Cp degrees 2Mo2P4S] (Cp degrees=1-tBu-3,4-Me2C5H2), P4S3 and Cu2I2 Building Blocks. EUROPEAN JOURNAL OF INORGANIC CHEMISTRY (6). pp. 785-793. ISSN 1434-1948,

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Abstract

The synthesis and characterization of [Cp degrees 2Mo2P4S] (1) and [Cp degrees 2Mo2P2S3] (2) (Cp degrees = 1-tBu-3,4-Me2C5H2) has been described. The reaction of 1 in CH2Cl2 with 2 equiv. of CuI in MeCN under diffusion conditions gave [(Cp degrees 2Mo2P4S)(3)-(CuI)(4)](n) (6a). The crystal structure of 6a consists of helical substructures of opposed chirality which are formed by the coordination of two Cu2I2 rings to three phosphorus atoms of the cyclo-P4S middle deck of 1. The resulting helix is connected with four helices of the same chirality by front-backside P coordination of another 1 unit. Compound 6a can reversibly include or release CH2Cl2 molecules without loosing its crystalline character. Thus, storing crystals of 6a under CH2Cl2 results in the formation of 6a center dot 0.55CH(2)Cl(2) (6b), the unit cell volume increasing by 113.6 angstrom(3) per formula unit, while in high vacuum the unit cell volume of 6b decreases to the value of 6a. The reaction of 1 with CuI in the presence of P4S3 gave a mixture of two isomeric polymers 7 and 8 of composition [(Cp degrees 2Mo2P4S)(P4S3)(CuI)(2)](n). The crystal structures of both compounds 7 and 8 contain linear strands of [1(CuI)(2)](n) and [(P4S3)(CuI)(2)](n) with planar Cu2I2 rings as common interface. A two-dimensional framework is formed by interpenetration of both types of strands. The analogous reaction of the mixture of [Cp-2*Mo2P4S] (Cp* = C5Me5) and P4S3 with CuI gave [(Cp-2*Mo2P4S)(P4S3)(CuI)(2)](n) (9). Contrary to the structures of 7 and 8 in this compound coordination of adjacent P atoms of the eta(3)-P-3 ligand and the eta(2)-PS dumbbell leads to the formation of one-dimensional ribbons.

Item Type: Article
Uncontrolled Keywords: X-RAY-STRUCTURE; COORDINATION CHEMISTRY; SELENIUM INTERACTIONS; COPPER(I) COMPLEXES; LIGAND COMPLEXES; CLUSTER; CRYSTAL; PENTAPHOSPHAFERROCENE; POLYMER; CHAINS; Metal-organic frameworks; Coordination polymers; Molybdenum; Copper; Phosphorus; Sulfur
Subjects: 500 Science > 540 Chemistry & allied sciences
500 Science > 570 Life sciences
Divisions: Biology, Preclinical Medicine > Institut für Biophysik und physikalische Biochemie > Prof. Dr. Dr. Hans Robert Kalbitzer
Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Manfred Scheer
Chemistry and Pharmacy > Institut für Anorganische Chemie > Alumni or Retired Professors > Arbeitskreis Dr. Joachim Wachter
Depositing User: Dr. Gernot Deinzer
Date Deposited: 26 Jun 2020 10:59
Last Modified: 26 Jun 2020 10:59
URI: https://pred.uni-regensburg.de/id/eprint/21347

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