TY - JOUR

T1 - Solvatomorphs of (Bu4N)2[{Ag(N2-py)}2Mo8O26]: structure, colouration and phase transition

AU - Abramov, Pavel A.

AU - Komarov, Vladislav Yu

AU - Pischur, Denis A.

AU - Sulyaeva, Veronica S.

AU - Benassi, Enrico

AU - Sokolov, Maxim N.

N1 - Funding Information: This work was supported by the grant of the President of the Russian Federation for young scientists - Doctors of sciences MD-396.2021.1.3. The authors are grateful to the Siberian Supercomputer Centre of Institute of Computational Mathematics and Mathematical Geophysics (Russian Academy of Sciences, Novosibirsk, Russian Federation) for kindly providing the computational resources; the technical staff of the Institute are also thanked for the assistance. The NIIC team thanks the Ministry of Science and Higher Education of the Russian Federation for the access to XRD (grant number 121031700313-8) and SEM (grant number 121031700314-5) facilities. The authors thank A. V. Chupina for the help with synthesis data collection. Funding Information: This work was supported by the grant of the President of the Russian Federation for young scientists – Doctors of sciences MD-396.2021.1.3. The authors are grateful to the Siberian Supercomputer Centre of Institute of Computational Mathematics and Mathematical Geophysics (Russian Academy of Sciences, Novosibirsk, Russian Federation) for kindly providing the computational resources; the technical staff of the Institute are also thanked for the assistance. The NIIC team thanks the Ministry of Science and Higher Education of the Russian Federation for the access to XRD (grant number 121031700313-8) and SEM (grant number 121031700314-5) facilities. The authors thank A. V. Chupina for the help with synthesis data collection. Publisher Copyright: © The Royal Society of Chemistry 2021.

PY - 2021/12/28

Y1 - 2021/12/28

N2 - Self-assembly of (Bu4N)4[β-Mo8O26], AgNO3and N2-py (N2-py = 2,6-diaminopyridine) in DMF solution results in a (Bu4N)2[β-{Ag(N2-py)}2Mo8O26] complex which crystallises as two phases: one (OP) is orange in colour and consists of [β-{Ag(N2-py)}2Mo8O26]2−monomers and [β-{Ag(N2-py)}2Mo8O26]n2n−polymeric chains in the crystal structure; the other (YP) is yellow in colour and built only with [β-{Ag(N2-py)}2Mo8O26]2−monomers. Both complexes were characterised by single crystal X-ray diffraction (SCXRD), X-ray powder diffraction (XRPD), diffuse reflectance (DR), infrared spectroscopy (IR), elemental analysis, and quantum chemical calculations. According to differential scanning calorimetry (DSC) and DR,OPdemonstrates a complicated phase transition at 130 K. Comprehensive SCXRD studies of the crystal structure change show rearrangement of the Ag+coordination sphere related with the dominant Ag-N bond distance change. TGA of both complexes confirms formation of silver nanoparticles (Ag-NPs), MoO3and Ag2Mo4O13upon thermal decomposition. The Ag-NPs were studied by SEM. Exfoliation of the resulting mixture in water gives a Ag-NP and MoO3mixed colloid system studied by TEM.

AB - Self-assembly of (Bu4N)4[β-Mo8O26], AgNO3and N2-py (N2-py = 2,6-diaminopyridine) in DMF solution results in a (Bu4N)2[β-{Ag(N2-py)}2Mo8O26] complex which crystallises as two phases: one (OP) is orange in colour and consists of [β-{Ag(N2-py)}2Mo8O26]2−monomers and [β-{Ag(N2-py)}2Mo8O26]n2n−polymeric chains in the crystal structure; the other (YP) is yellow in colour and built only with [β-{Ag(N2-py)}2Mo8O26]2−monomers. Both complexes were characterised by single crystal X-ray diffraction (SCXRD), X-ray powder diffraction (XRPD), diffuse reflectance (DR), infrared spectroscopy (IR), elemental analysis, and quantum chemical calculations. According to differential scanning calorimetry (DSC) and DR,OPdemonstrates a complicated phase transition at 130 K. Comprehensive SCXRD studies of the crystal structure change show rearrangement of the Ag+coordination sphere related with the dominant Ag-N bond distance change. TGA of both complexes confirms formation of silver nanoparticles (Ag-NPs), MoO3and Ag2Mo4O13upon thermal decomposition. The Ag-NPs were studied by SEM. Exfoliation of the resulting mixture in water gives a Ag-NP and MoO3mixed colloid system studied by TEM.

UR - http://www.scopus.com/inward/record.url?scp=85121514413&partnerID=8YFLogxK

U2 - 10.1039/d1ce01152a

DO - 10.1039/d1ce01152a

M3 - Article

AN - SCOPUS:85121514413

VL - 23

SP - 8527

EP - 8537

JO - CrystEngComm

JF - CrystEngComm

SN - 1466-8033

IS - 48

ER -