TY - JOUR
T1 - Emission and theoretical studies of Schiff-base [2+2] macrocycles derived from 2,2′-oxydianiline and zinc complexes thereof
AU - Wang, Kuiyuan
AU - Chen, Kai
AU - Bian, Tiezheng
AU - Chao, Yimin
AU - Yamato, Takehiko
AU - Xing, Feng
AU - Prior, Timothy J.
AU - Redshaw, Carl
PY - 2021/6
Y1 - 2021/6
N2 - The emission properties of a number of solvates of the [2 + 2] Schiff-base macrocycles {[2-(OH)-5-(R)–C
6H
2–1,3-(CH)
2][O(2-C
6H
4N)
2]}
2 (Me L
1H
2, tBu L
2H
2, Cl L
3H
2), formed by reacting 2,6-dicarboxy-4-R-phenol with 2,2′-oxydianiline (2-aminophenylether), (2-NH
2C
6H
4)
2O, have been investigated. Macrocycles L
1−3H
2 exhibited different maximum emission wavelengths in different solvents, from λ
max at 508 nm (in acetonitrile) to 585 nm (in dichloromethane). DFT studies on systems L
1−3H
2 involving solvents of different polarity (DMF versus n-hexane) indicated that the energy level gap increases with solvent polarity in line with the observed hypochromic shifts. Reaction of macrocycle L
1H
2 with three equivalents of ZnBr
2, in the presence of Et
3N, affords the complex [(ZnBr)(ZnNCMe)L
1]
2[ZnBr
4]·2.5MeCN (1·2.5MeCN). In the case of L
2H
2, reaction with two equivalents of ZnBr
2 affords [(ZnBr)L
2H
2][ZnBr
3NCMe]·3MeCN (2·3MeCN), whilst in the presence of two equivalents of Et
3N, work-up led to the isolation of the complex [(ZnBr)
2L
2]·4.5MeCN (3·4.5MeCN). The molecular structures of 1, 2 and 3 are reported, together with their emission behaviour.
AB - The emission properties of a number of solvates of the [2 + 2] Schiff-base macrocycles {[2-(OH)-5-(R)–C
6H
2–1,3-(CH)
2][O(2-C
6H
4N)
2]}
2 (Me L
1H
2, tBu L
2H
2, Cl L
3H
2), formed by reacting 2,6-dicarboxy-4-R-phenol with 2,2′-oxydianiline (2-aminophenylether), (2-NH
2C
6H
4)
2O, have been investigated. Macrocycles L
1−3H
2 exhibited different maximum emission wavelengths in different solvents, from λ
max at 508 nm (in acetonitrile) to 585 nm (in dichloromethane). DFT studies on systems L
1−3H
2 involving solvents of different polarity (DMF versus n-hexane) indicated that the energy level gap increases with solvent polarity in line with the observed hypochromic shifts. Reaction of macrocycle L
1H
2 with three equivalents of ZnBr
2, in the presence of Et
3N, affords the complex [(ZnBr)(ZnNCMe)L
1]
2[ZnBr
4]·2.5MeCN (1·2.5MeCN). In the case of L
2H
2, reaction with two equivalents of ZnBr
2 affords [(ZnBr)L
2H
2][ZnBr
3NCMe]·3MeCN (2·3MeCN), whilst in the presence of two equivalents of Et
3N, work-up led to the isolation of the complex [(ZnBr)
2L
2]·4.5MeCN (3·4.5MeCN). The molecular structures of 1, 2 and 3 are reported, together with their emission behaviour.
KW - DFT studies
KW - Emission
KW - Macrocycle
KW - Schiff-base
KW - Solvents
UR - http://www.scopus.com/inward/record.url?scp=85104132009&partnerID=8YFLogxK
U2 - 10.1016/j.dyepig.2021.109300
DO - 10.1016/j.dyepig.2021.109300
M3 - Article
VL - 190
JO - Dyes and Pigments
JF - Dyes and Pigments
SN - 0143-7208
M1 - 109300
ER -