Issue 10, 2022

Structural control in the nanoassembly of the tungsten and molybdenum dithiolene complex analog

Abstract

Structural control at the nanoscale via self-assembly toward ordered and well-defined material hierarchies is a critical aspect for the fabrication of functional nanostructures. Herein, the tunable manipulation of the self-assembly of dithiolene complexes to controlled morphology directed by concentration variation is reported. Dimeric tungsten(V) (1) and molybdenum(V) (2) dithiolene–diamide complexes were synthesized and structurally characterized by the single-crystal X-ray diffraction method. Interestingly, the trans-(W2S4) core is present in 1 in contrast to the cis-(Mo2S4) core in 2 in these analogous complexes. DFT calculations show that the trans form of 1 is stabilized from its cis form by 8 kcal mol−1, whereas the stable cis form of 2 is stabilized from its trans form by 30 kcal mol−1. This variation in the positional terminal sulfide ligand in 1 and 2 is reflected in the respective lattice packing. Such packing controls the self-assembly process to aggregate into different floral shapes in the nanodomain and on increasing the concentration of 1 or 2 results in nanopolyhedral shapes. Such structural control of concentration-driven self-assemblies provides future opportunities to engineer technologically desired nanostructures with complex architectures.

Graphical abstract: Structural control in the nanoassembly of the tungsten and molybdenum dithiolene complex analog

Supplementary files

Article information

Article type
Paper
Submitted
21 Mud 2022
Accepted
04 Maw 2022
First published
04 Maw 2022

React. Chem. Eng., 2022,7, 2231-2239

Structural control in the nanoassembly of the tungsten and molybdenum dithiolene complex analog

J. Bhuyan, B. Pakhira, A. Begum, S. Sarkar and K. M. Tripathi, React. Chem. Eng., 2022, 7, 2231 DOI: 10.1039/D2RE00205A

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