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Self-Assembly of Metallamacrocycles Using a Dinuclear Organometallic Acceptor: Synthesis, Characterization, and Sensing Study

Shanmugaraju, Sankarasekaran and Joshi, Sachin A and Mukherjee, Partha Sarathi (2011) Self-Assembly of Metallamacrocycles Using a Dinuclear Organometallic Acceptor: Synthesis, Characterization, and Sensing Study. In: Inorganic Chemistry, 50 (22). pp. 11736-11745.

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Official URL: http://pubs.acs.org/doi/abs/10.1021/ic201745y

Abstract

A dinuclear organometallic acceptor 4,4'-bis[trans-Pt(PEt(3))(2)(O(3)SCF(3))(ethynyl)]biphenyl (1) containing Pt-ethynyl functionality is synthesized. Multinuclear NMR ((1)H, (31)P, and (13)C), infrared (IR), and electrospray ionization mass spectrometry (ESI-MS) including single-crystal X-ray diffraction analysis established the formation of 1. Equimolar treatment of acceptor 1 separately with three different ``clip'' type ditopic donors (L(a)-L(c)) yielded [2 + 2] self-assembled three metallamacrocycles 2a-2c, respectively. These macrocycles were characterized by various spectroscopic techniques, and their sizes/shapes were obtained through geometry optimization using molecular mechanics universal force field (MMUFF) simulations. Attachment of unsaturated ethynyl functionality to biphenyl building unit helped to make the macrocycles (2a-2c) pi-electron rich and thereby fluorescent in nature. Furthermore, 2c in solution has been examined to be suitable for sensing electron-deficient nitroaromatic like picric acid, which is often considered as a secondary chemical explosive. The fluorescence study of 2c showed a marked quenching of initial emission intensity upon titrating with picric acid (PA), and it exhibited the largest fluorescence quenching response with high selectivity among various other electron deficient aromatic compounds tested.

Item Type: Journal Article
Additional Information: Copyright of this article belongs to American Chemical Society.
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Depositing User: Id for Latest eprints
Date Deposited: 19 Dec 2011 11:50
Last Modified: 19 Dec 2011 11:50
URI: http://eprints.iisc.ac.in/id/eprint/42771

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