TY - JOUR
T1 - Reversible single-crystal to single-crystal phase transformation between a new Werner clathrate and its apohost
AU - Matos, Catiúcia R.M.O.
AU - Sanii, Rana
AU - Wang, Shi Qiang
AU - Ronconi, Célia M.
AU - Zaworotko, Michael J.
N1 - Publisher Copyright:
© 2021 The Royal Society of Chemistry.
PY - 2021/10/7
Y1 - 2021/10/7
N2 - In this work, we report the synthesis and structural characterisation of the ligand 2-(pyridin-3-yl)-benzo[de]isoquinoline-1,3(2H)-dione, 5, its isostructural Werner complexes ML4(NCS)2 (L = 5; M = Co(ii) and Ni(ii)), and five clathrates with three aromatic guests, ML4(NCS)2·2G (M = Co(ii) and Ni(ii), G = nitrobenzene (NB); M = Co, G = 1,2-dichlorobenzene (1,2-DCB); M = Co(ii) and Ni(ii), G = o-xylene (OX)). 5 was prepared in high yield by condensation in the solid-state (C3S3, Cocrystal Controlled Solid-State Synthesis). The Werner complexes ML4(NCS)2 (M = Co(ii) and Ni(ii)) (apohosts) were prepared by reacting M(NCS)2 (M = Co(ii) and Ni(ii)) and 5 in 1-butanol at 60 °C for 24 h. The Werner clathrates were prepared by reacting M(NCS)2 (M = Co(ii) and Ni(ii)), G and 5 in 1-butanol at 60 °C for 48-96 h. The clathrates were observed to transform to the apohost ML4(NCS)2 upon heating. CoL4(NCS)2·2NB was subsequently regenerated by exposing CoL4(NCS)2 to liquid NB at 60 °C for 48 h. This phase change occurred as a single-crystal to single-crystal phase transformation and was studied by single crystal X-ray diffraction, powder X-ray diffraction and thermal analyses. Structural analyses of the apohost CoL4(NCS)2 and its Werner clathrate CoL4(NCS)2·2NB indicated that rotational freedom of the Co-N bonds together with torsional flexibility of the ligand between the imide bond and the pyridine moiety are key to enabling the structural switching induced by exposure to NB or its removal.
AB - In this work, we report the synthesis and structural characterisation of the ligand 2-(pyridin-3-yl)-benzo[de]isoquinoline-1,3(2H)-dione, 5, its isostructural Werner complexes ML4(NCS)2 (L = 5; M = Co(ii) and Ni(ii)), and five clathrates with three aromatic guests, ML4(NCS)2·2G (M = Co(ii) and Ni(ii), G = nitrobenzene (NB); M = Co, G = 1,2-dichlorobenzene (1,2-DCB); M = Co(ii) and Ni(ii), G = o-xylene (OX)). 5 was prepared in high yield by condensation in the solid-state (C3S3, Cocrystal Controlled Solid-State Synthesis). The Werner complexes ML4(NCS)2 (M = Co(ii) and Ni(ii)) (apohosts) were prepared by reacting M(NCS)2 (M = Co(ii) and Ni(ii)) and 5 in 1-butanol at 60 °C for 24 h. The Werner clathrates were prepared by reacting M(NCS)2 (M = Co(ii) and Ni(ii)), G and 5 in 1-butanol at 60 °C for 48-96 h. The clathrates were observed to transform to the apohost ML4(NCS)2 upon heating. CoL4(NCS)2·2NB was subsequently regenerated by exposing CoL4(NCS)2 to liquid NB at 60 °C for 48 h. This phase change occurred as a single-crystal to single-crystal phase transformation and was studied by single crystal X-ray diffraction, powder X-ray diffraction and thermal analyses. Structural analyses of the apohost CoL4(NCS)2 and its Werner clathrate CoL4(NCS)2·2NB indicated that rotational freedom of the Co-N bonds together with torsional flexibility of the ligand between the imide bond and the pyridine moiety are key to enabling the structural switching induced by exposure to NB or its removal.
UR - http://www.scopus.com/inward/record.url?scp=85116553571&partnerID=8YFLogxK
U2 - 10.1039/d1dt01839f
DO - 10.1039/d1dt01839f
M3 - Article
C2 - 34581342
AN - SCOPUS:85116553571
SN - 1477-9226
VL - 50
SP - 12923
EP - 12930
JO - Dalton Transactions
JF - Dalton Transactions
IS - 37
ER -