Research output: Contribution to journal › Article › peer-review
[{AgL}2Mo8O26]n- complexes : A combined experimental and theoretical study. / Chupina, Anastasia V.; Shayapov, Vladimir; Novikov, Alexander S. et al.
In: Dalton Transactions, Vol. 49, No. 5, 01.01.2020, p. 1522-1530.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - [{AgL}2Mo8O26]n- complexes
T2 - A combined experimental and theoretical study
AU - Chupina, Anastasia V.
AU - Shayapov, Vladimir
AU - Novikov, Alexander S.
AU - Volchek, Victoria V.
AU - Benassi, Enrico
AU - Abramov, Pavel A.
AU - Sokolov, Maxim N.
PY - 2020/1/1
Y1 - 2020/1/1
N2 - Self-assembly reactions between AgNO3, L (PPh3, PPh2Py, AsPh3, SbPh3) and [β-Mo8O26]4- in DMF led to the formation of [β-{AgL}2Mo8O26]2- anions, which were isolated as Bu4N+ salts (1-4) and characterized by XRD, IR and elemental analysis. In the crystal structures Ag+ can switch the coordination number from 5 (P, As) to 6 (Sb) by uptake of a DMF molecule. High-level QAIM analysis of the coordination sphere around Ag shows critical points even in the case of longer Ag-O distances. Changing the ligand type to a family of substituted pyridines results in novel Ag-L-POM complexes with different environments around Ag+. For 3-X-pyridine ligands (X = Cl, Br, I), complexes with additional DMF molecules [β-{AgL(DMF)}2Mo8O26]2- (5-7) have been isolated. Halogen bonding of the X⋯O type was detected in the crystal structures of 5-7 and studied by DFT calculations, providing estimated energies from 0.9 to 3.4 kcal mol-1. Variation of substituents at the pyridine ring results in the formation of [β-{AgL}2Mo8O26]2- in the case of 2-NH2-py (8), 2-CH3-Py (9), 2,4,6-collidine (10) and 2,6-NH2-py (11). Solution behavior of 1-4 in CH3CN was studied by a hyphenated HPLC-ICP-AES technique. According to the results, the [β-{AgL}2Mo8O26]2- anions are largely dissociated in this medium. An attempt to change the [Mo8O26]4- precursor to [Mo6O19]2- (in the case of AgNO3 and PyPPh2) resulted in the crystallization of [Ag2(PyPPh2)2(DMF)4][Mo6O19] (12).
AB - Self-assembly reactions between AgNO3, L (PPh3, PPh2Py, AsPh3, SbPh3) and [β-Mo8O26]4- in DMF led to the formation of [β-{AgL}2Mo8O26]2- anions, which were isolated as Bu4N+ salts (1-4) and characterized by XRD, IR and elemental analysis. In the crystal structures Ag+ can switch the coordination number from 5 (P, As) to 6 (Sb) by uptake of a DMF molecule. High-level QAIM analysis of the coordination sphere around Ag shows critical points even in the case of longer Ag-O distances. Changing the ligand type to a family of substituted pyridines results in novel Ag-L-POM complexes with different environments around Ag+. For 3-X-pyridine ligands (X = Cl, Br, I), complexes with additional DMF molecules [β-{AgL(DMF)}2Mo8O26]2- (5-7) have been isolated. Halogen bonding of the X⋯O type was detected in the crystal structures of 5-7 and studied by DFT calculations, providing estimated energies from 0.9 to 3.4 kcal mol-1. Variation of substituents at the pyridine ring results in the formation of [β-{AgL}2Mo8O26]2- in the case of 2-NH2-py (8), 2-CH3-Py (9), 2,4,6-collidine (10) and 2,6-NH2-py (11). Solution behavior of 1-4 in CH3CN was studied by a hyphenated HPLC-ICP-AES technique. According to the results, the [β-{AgL}2Mo8O26]2- anions are largely dissociated in this medium. An attempt to change the [Mo8O26]4- precursor to [Mo6O19]2- (in the case of AgNO3 and PyPPh2) resulted in the crystallization of [Ag2(PyPPh2)2(DMF)4][Mo6O19] (12).
KW - CRYSTAL-STRUCTURE
KW - NONCOVALENT INTERACTIONS
KW - HALOGEN
KW - APPEARANCE
KW - CONTACTS
KW - GROWTH
KW - DONOR
KW - SALTS
KW - AG
KW - PD
UR - http://www.scopus.com/inward/record.url?scp=85079076224&partnerID=8YFLogxK
U2 - 10.1039/c9dt04043a
DO - 10.1039/c9dt04043a
M3 - Article
C2 - 31930239
AN - SCOPUS:85079076224
VL - 49
SP - 1522
EP - 1530
JO - Dalton Transactions
JF - Dalton Transactions
SN - 1477-9226
IS - 5
ER -
ID: 23425911