TY - JOUR
T1 - Polyoxometalate-Induced Preorganization of Halogenated Ligands in Supramolecular Assemblies
AU - Choudhari, Manjiri
AU - McDonald, Peter W.
AU - Ritchie, Chris
N1 - Funding Information:
C.R. would like to thank Monash University and the Australian Research Council for funding this research (FT180100610). C.R. also acknowledges the funding support from the Australian Research Council for the ARC Centre of Excellence for Enabling Eco-Efficient Beneficiation of Minerals, grant no. CE200100009. M.C. thanks the School of Chemistry, Monash University, for DPRS and DIPRS scholarships. P.W.M. thanks the School of Chemistry, Monash University, and the Australian Government for the RTP scholarship. Dr. Alasdair McKay and Dr. Adam Kennedy are thanked for their valuable feedback on the NMR experiments.
Publisher Copyright:
© 2024 The Authors. Published by American Chemical Society
PY - 2024/2/7
Y1 - 2024/2/7
N2 - Research on polyoxometalates (POMs) with the Keggin structure has been ongoing for several decades. However, the trilacunary phosphomolybdate derivative was difficult to obtain until recently. By using pyridine in nonaqueous media, stabilization of the trilacunary phosphomolybdate was achieved, and the six terminal ligand sites within the structural vacancy alternated between oxido and pyridyl ligands. Through ligand exchange experiments, we were able to control the intramolecular spatial separation of coordinated halogenated ligands as well as intermolecular halogen-halogen interactions in the crystalline state. Our results reveal a new X6 synthon (where X = Cl, Br, and I) and a desolvation-induced single-crystal to single-crystal transition.
AB - Research on polyoxometalates (POMs) with the Keggin structure has been ongoing for several decades. However, the trilacunary phosphomolybdate derivative was difficult to obtain until recently. By using pyridine in nonaqueous media, stabilization of the trilacunary phosphomolybdate was achieved, and the six terminal ligand sites within the structural vacancy alternated between oxido and pyridyl ligands. Through ligand exchange experiments, we were able to control the intramolecular spatial separation of coordinated halogenated ligands as well as intermolecular halogen-halogen interactions in the crystalline state. Our results reveal a new X6 synthon (where X = Cl, Br, and I) and a desolvation-induced single-crystal to single-crystal transition.
UR - http://www.scopus.com/inward/record.url?scp=85184771435&partnerID=8YFLogxK
U2 - 10.1021/acs.cgd.3c00861
DO - 10.1021/acs.cgd.3c00861
M3 - Article
AN - SCOPUS:85184771435
SN - 1528-7483
VL - 24
SP - 932
EP - 937
JO - Crystal Growth & Design
JF - Crystal Growth & Design
IS - 3
ER -