Issue 10, 2008
From the journal:

CrystEngComm

Engineering delocalizing π electronic [CuII3(μ3-OH)(μ-pz)3]2+ species into organometallic frameworks by Ag-π coordination†

Ling-Ling Zheng,a   Ji-Dong Leng,a   Shao-Liang Zheng,b   Yong-Cuo Zhaxi,a   Wei-Xiong Zhanga  and  Ming-Liang Tong*a  

* Corresponding authors

a MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou, China
E-mail: tongml@mail.sysu.edu.cn

b Department of Chemistry, State University of New York at Buffalo, Buffalo, New York, USA

Abstract

Reactions of [CuII3(μ3-OH)(μ-pz)3]2+-containing precursor [{Cu3(μ3-OH)(μ-pz)3(Hpz)3}2(μ6-SO4)](NO3)2·MeCN·MeOH·1.5H2O (1) with silver salts under mild conditions generate two novel Cu(II)–Ag(I) organometallic solids involving the 4-position C atom of pz− ligand bonded to the Ag centers, [Ag(Hpz)2]2[{Ag2(Hpz)2(NO3)2}{Cu6(OH)2(pz)6(Hpz)6(SO4)}2](NO3)6·4H2O (2) and [{Ag(H2O)2}{Cu3(OH)(pz)3(Hpz)3(H2O)(ClO4)3}]n (3). 1 has a 1D coordination chain structure constructed with hexanuclear cluster units and μ-nitrate bridges. A pair of [CuII3(μ3-OH)(μ-pz)3(Hpz)3]2+ units bridged by one μ3-SO42−group constitutes the hexanuclear cluster. 2 contains 0D organometallic Ag2Cu12 cluster cations formed by a pair of [{Cu3(OH)(pz)3(Hpz)3}2(μ4-SO4)]2+cluster units and one neutral Ag2(Hpz)2(NO3)2 unit viaAg-π(pz−) and Ag–O(NO3−) coordination, [Ag(Hpz)2]+ cations and nitrate anions as well as lattice water molecules. 3 contains 1D neutral organometallic chains constructed with anionic [Cu3(OH)(pz)3(Hpz)3(H2O)(ClO4)3]−cluster units and cationic [Ag(H2O)2]+ units viaAg-π(pz−) coordination. MO calculations based on the {[Cu3(OH)(pz)3(Hpz)3]–[Ag(H2O)2]–[Cu3(OH)(pz)3(Hpz)3]}5+ cation model with the related X-ray geometry were carried out. The Mayer bond orders of the Ag–C are calculated to be 0.249 and 0.275, showing that the Ag(I)- η1-C orbital interactions are significantly attractive. A Bader analysis of the electron density further shows the presence of a (3,−1) bond-critical point linking the Ag(I) and C atoms and 1.366/1.378 Å away from Ag(I), which further confirms the existence of Ag(I)–C bonding between the fragments. The magnetic properties of 1–3 were also studied.

Graphical abstract: Engineering delocalizing π electronic [CuII3(μ3-OH)(μ-pz)3]2+ species into organometallic frameworks by Ag-π coordination

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Article information

DOI
https://doi.org/10.1039/B806202A
Article type
Paper
Submitted
14 Apr 2008
Accepted
11 Jul 2008
First published
05 Aug 2008

CrystEngComm, 2008,10, 1467-1473

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Engineering delocalizing π electronic [CuII3(μ3-OH)(μ-pz)3]2+ species into organometallic frameworks by Ag-π coordination

L. Zheng, J. Leng, S. Zheng, Y. Zhaxi, W. Zhang and M. Tong, CrystEngComm, 2008, 10, 1467 DOI: 10.1039/B806202A

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