Investigation of structure-directing interactions within copper(i)thiocyanate complexes through X-ray analyses and non-covalent interaction (NCI) theoretical approach

Khodayar Gholivand,Mahdieh Hosseini,Kaveh Farshadfar,S Mark Roe,Akram Gholami

doi:10.1039/c6ce01339b

Khodayar Gholivand, Mahdieh Hosseini + Show 3 more

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https://doi.org/10.1039/c6ce01339b

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Journal: CrystEngComm	Publication Date: Jan 1, 2016
Citations: 20	License type: cc-by

Affiliation: Tarbiat Modares University, University of Sussex

Abstract

Herein, we reported the synthesis of copper(I) thiocyanate complexes with ortho-pyridinyl carbohydrazones containing a thiophene (L1) or a furyl ring (L2) as a mixture of two different crystals for each compound, linkage isomers of C1N, [Cu(NCS)(L1)PPh3] and C1S, [Cu(SCN)(L1)PPh3], for L1, whereas monomeric and polymeric structures C2N, [Cu(NCS)(L2)PPh3], and C2P, [–(NCS)Cu(L2)–]n, for L2. Crystallographic information and theoretical calculations, mainly noncovalent interaction reduced density gradient (NCI-RDG) analyses, were pursued to generate a profound understanding of the structure-directing interactions in these complexes. The supramolecular assemblies are first driven by cooperative π⋯π interactions and hydrogen bonds followed by CH⋯π, S⋯S and S⋯π linkages. In the case of the linkage isomers, intermolecular interactions may have a significant role in the formation of the less stable S-bound isomer C1S.

Highlights

IntroductionCopperIJI) compounds have attracted a growing interest because of their high structural diversity,[1,2,3,4] catalytic activity[5,6,7] and photophysical properties.[3,8,9,10] They have applications in different areas such as organic light-emitting diodes (OLEDs),[11,12,13,14,15,16,17,18,19,20,21,22] supramolecular assemblies, oxygen sensors and biological probes
The rich structural features and utilitarian considerations have motivated researchers to focus on the synthesis and characterization of CuIJI) complexes with various donor ligands
Paper ortho-pyridinyl carbohydrazones containing a thiophene (L1) or a furyl ring (L2); see Scheme 1. The former resulted in two linkage isomers: C1N [CuIJNCS)IJL1)PPh3] and C1S [Cu(SCN)(L1)PPh3], while the later afforded monomeric and polymeric complexes of C2N [Cu(NCS)(L2)PPh3] and C2P [–(NCS)Cu(L2)–]n

Summary

Introduction

CopperIJI) compounds have attracted a growing interest because of their high structural diversity,[1,2,3,4] catalytic activity[5,6,7] and photophysical properties.[3,8,9,10] They have applications in different areas such as organic light-emitting diodes (OLEDs),[11,12,13,14,15,16,17,18,19,20,21,22] supramolecular assemblies, oxygen sensors and biological probes. Paper ortho-pyridinyl carbohydrazones containing a thiophene (L1) or a furyl ring (L2); see Scheme 1 The former resulted in two linkage isomers: C1N [CuIJNCS)IJL1)PPh3] and C1S [Cu(SCN)(L1)PPh3], while the later afforded monomeric and polymeric complexes of C2N [Cu(NCS)(L2)PPh3] and C2P [–(NCS)Cu(L2)–]n. We have used a recently introduced alternative interpretive technique, the non-covalent interaction (NCI) approach, to manifest the diverse NCIs at the crystal packing structures. This method is based on the analysis of the electron density and enables us to identify and visualize the interactions.[32] Various non-covalent interactions, including hydrogen bonding,[33] S⋯S, S⋯π,34 π⋯π35 and CH⋯π36 interactions, have been investigated in this work

Results and discussion

Conclusions

Materials and methods

Synthesis procedures