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. Author manuscript; available in PMC: 2024 Jun 7.
Published in final edited form as: J Am Chem Soc. 2023 Dec 27;146(1):500–513. doi: 10.1021/jacs.3c09983

Table 5.

DFT-calculated X-Cu-N1 bond angles and relative energies for the [Cu(ibaps)L]n and [Cu(ibapsT)X]n complexes.a

Complex 1-L 2-L (broken symmetry) 2-L (ferromagnetic) ΔEc 3-L
[Cu(ibaps)OH2]n 166 171 172 −450 172
[Cu(ibapsT)OH2]n 131d 137 180 370 176
[Cu(ibaps)TMG]n 156 153 162 830 158
[Cu(ibaps)DBU]n 147 143 165 560 149
[Cu(ibapsT)DBU]n 159 152 180 532 179
[Cu(ibaps)TBD]n 137 144 152 1070 152
[Cu(ibapsT)TBD]n,b 123 140 175 581 179
[Cu(ibapsT)N(H)CH2]n,b 156 141 180 800 178
[Cu(ibapsT)NH3]n 156 145 178 491 175
a

T is truncated ligand with the sulfonamido aryl groups replaced by hydrogen atoms. Angles in degrees. Broken symmetry refers to antiparallel spins, and ferromagnetic refers to complexes with the S = 1 spin ground state. For selected computed bond lengths in 1-X and 2-X (X = OH2 and DBU) see Table S10.

b

During optimization, the imine and TBD plane was kept orthogonal to the ibaps plane by imposing suitable dihedral constraints (see Supporting Information).

c

Difference in the energies of the ferromagnetic and the broken symmetry states, Ererro - EBroken Symm, in wavenumbers.

d

In this optimization, one of the lone pairs of the water ligand was directed toward the Cu throughout the optimization by imposing suitable angular and dihedral constraints (see Supporting Information).