TY - JOUR
T1 - Enhanced and Heteromolecular Guest Encapsulation in Nonporous Crystals of a Perfluorinated Triketonato Dinuclear Copper Complex
AU - Ikumura, Yoshinori
AU - Habuka, Yusuke
AU - Sakai, Shunichiro
AU - Shinohara, Takanori
AU - Yuge, Hidetaka
AU - Rzeznicka, Izabela I.
AU - Hori, Akiko
N1 - Funding Information:
This work was supported by Grant‐in‐Aid for Scientific Research C (No.18K05153 and 18K03548) of JSPS KAKENHI.
Publisher Copyright:
© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2020/4/16
Y1 - 2020/4/16
N2 - The flexible host framework of a perfluorinated mononuclear copper complex, [Cu(L1)2] (1, HL1=3-hydroxy-1,3-bis(pentafluorophenyl)-2-propen-1-one), with a CuO4 core reversibly encapsulated several organic guest molecules through electrostatic interactions in its crystals. Hence, the corresponding dinuclear complex, [Cu2(L2)2] (2, H2L2=1,5-dihydroxy-1,5-bis(pentafluorophenyl)-1,4-pentadien-3-one), was prepared to enhance guest recognition and the ability to separate molecular mixtures. Complex 2 comprises a Cu2O6 core and four pentafluorophenyl groups. In crystal 2, cavities are formed on the axial sites of the metal core that are surrounded by pentafluorophenyl groups. The crystal of 2 encapsulates various guest molecules, that is, benzene (3), toluene (4), xylene (5), mesitylene (6), durene (7), and anisole (8). X-ray crystallographic and thermogravimetric (TG) studies show that three guest molecules are present in the crystal cavities. The number of guest molecules found in complex 2 was higher than that in complex 1, for example, (2)3⋅(6)10>1⋅(6)2, (2)2⋅(7)7>1⋅7, or 2⋅(8)3>1⋅(8)2. Naphthalene (9), was encapsulated in 2 to give 2⋅(9)3, but not in 1. In the crystal of complex 2, heteromolecular guest encapsulation was confirmed, designated as 2⋅(3)2⋅9. TG analysis indicates that the thermal stability of the guest-included crystals of 2 is higher than that of 1.
AB - The flexible host framework of a perfluorinated mononuclear copper complex, [Cu(L1)2] (1, HL1=3-hydroxy-1,3-bis(pentafluorophenyl)-2-propen-1-one), with a CuO4 core reversibly encapsulated several organic guest molecules through electrostatic interactions in its crystals. Hence, the corresponding dinuclear complex, [Cu2(L2)2] (2, H2L2=1,5-dihydroxy-1,5-bis(pentafluorophenyl)-1,4-pentadien-3-one), was prepared to enhance guest recognition and the ability to separate molecular mixtures. Complex 2 comprises a Cu2O6 core and four pentafluorophenyl groups. In crystal 2, cavities are formed on the axial sites of the metal core that are surrounded by pentafluorophenyl groups. The crystal of 2 encapsulates various guest molecules, that is, benzene (3), toluene (4), xylene (5), mesitylene (6), durene (7), and anisole (8). X-ray crystallographic and thermogravimetric (TG) studies show that three guest molecules are present in the crystal cavities. The number of guest molecules found in complex 2 was higher than that in complex 1, for example, (2)3⋅(6)10>1⋅(6)2, (2)2⋅(7)7>1⋅7, or 2⋅(8)3>1⋅(8)2. Naphthalene (9), was encapsulated in 2 to give 2⋅(9)3, but not in 1. In the crystal of complex 2, heteromolecular guest encapsulation was confirmed, designated as 2⋅(3)2⋅9. TG analysis indicates that the thermal stability of the guest-included crystals of 2 is higher than that of 1.
KW - copper
KW - crystal growth
KW - dinuclear compounds
KW - fluorinated substituents
KW - host–guest systems
KW - supramolecular chemistry
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U2 - 10.1002/chem.201905740
DO - 10.1002/chem.201905740
M3 - Article
C2 - 32026510
AN - SCOPUS:85082949297
SN - 0947-6539
VL - 26
SP - 5051
EP - 5060
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 22
ER -