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1 Copyright Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2003 Chem. Eur. J Supporting Information for Generation and Coupling of [Mn(dmpe) 2 (C CR)(C C)] Radicals Producing Redox-active C 4 -Bridged Rigid-rod Complexes Francisco J. Fernández, Koushik Venkatesan, Olivier Blacque, Montserrat Alfonso, Helmut W. Schmalle and Heinz Berke* Anorganisch-Chemisches Institut der Universität Zürich, Winterthurerstrasse 190, CH-8057 Zürich, Switzerland DFT Calculations ENERGIES AND CARTESIAN COORDINATES OF THE MODEL SYSTEM [{Mn(dHpe) 2 (C CH)} 2 (m-c 4 )] Mn P P C C P P C H C Mn P P P P C C C C C H H C H H C H H C H H C H H C H H C H H C H H H H H H H H H H H H H H H
2 H H H H hartree kcal/mol kj/mol Total Charge: 0.00 Spin Polarisation: 2.00 change in energy gradient max gradient rms Electrostatic Energy: Kinetic Energy: Coulomb (Steric+OrbInt) Energy: XC Energy: Solvation: ENERGIES AND CARTESIAN COORDINATES OF THE MODEL SYSTEM [{Mn(dHpe) 2 (C CH)} 2 (m-c 4 )] + Mn P P C C P P C H C Mn P P P P C C C C C H H C H H C H H C H H C H H C H H C H H C H H H H H H H H H H H H H
3 H H H H H H hartree kcal/mol kj/mol Total Charge: 1.00 Spin Polarisation: 1.00 change in energy gradient max gradient rms Electrostatic Energy: Kinetic Energy: Coulomb (Steric+OrbInt) Energy: XC Energy: Solvation: ENERGIES AND CARTESIAN COORDINATES OF THE MODEL SYSTEM [{Mn(dHpe) 2 (C CH)} 2 (m-c 4 )] 2+ Mn P P C C P P C H C Mn P P P P C C C C C H H C H H C H H C H H C H H C H H C H H C H H H H H H H H H H H H H
4 H H H H H H hartree kcal/mol kj/mol Total Charge: 2.00 change in energy gradient max gradient rms Electrostatic Energy: Kinetic Energy: Coulomb (Steric+OrbInt) Energy: XC Energy: Solvation: ENERGIES AND CARTESIAN COORDINATES OF THE MODEL SYSTEM [{Mn(dHpe) 2 (C CSiMe 3 )} 2 (m-c 4 )] Mn P P C C P P C Si C Mn P P P P C C C C C H H C H H C H H C H H C H H C H H C H H C H H H H H H H H H H H H H
5 H H H H H Si C C C C C C H H H H H H H H H H H H H H H H H H hartree kcal/mol kj/mol Total Charge: Spin Polarisation: 2.00 change in energy gradient max gradient rms Electrostatic Energy: Kinetic Energy: Coulomb (Steric+OrbInt) Energy: XC Energy: Solvation: ENERGIES AND CARTESIAN COORDINATES OF THE MODEL SYSTEM [{Mn(dHpe) 2 (C CSiMe 3 )} 2 (m-c 4 )] + Mn P P C C P P C Si C Mn P P P P C C C C C H H C H H C H H C H
6 H C H H C H H C H H C H H H H H H H H H H H H H H H H H H Si C C C C C C H H H H H H H H H H H H H H H H H H hartree kcal/mol kj/mol Total Charge: 1.00 Spin Polarisation: 1.00 change in energy gradient max gradient rms Electrostatic Energy: Kinetic Energy: Coulomb (Steric+OrbInt) Energy: XC Energy: Solvation: ENERGIES AND CARTESIAN COORDINATES OF THE MODEL SYSTEM [{Mn(dHpe) 2 (C CSiMe 3 )} 2 (m-c 4 )] 2+ Mn P P C C P
7 P C Si C Mn P P P P C C C C C H H C H H C H H C H H C H H C H H C H H C H H H H H H H H H H H H H H H H H H Si C C C C C C H H H H H H H H H H H H H H H H H H hartree kcal/mol kj/mol Total Charge: 2.00 change in energy gradient max gradient rms Electrostatic Energy: Kinetic Energy: Coulomb (Steric+OrbInt) Energy: XC Energy: Solvation:
8 ENERGIES AND CARTESIAN COORDINATES OF THE MODEL SYSTEM [{Mn(dHpe) 2 I} 2 (m-c 4 )] Mn P P C I P P C Mn P P P P I C C C H H C H H C H H C H H C H H C H H C H H C H H H H H H H H H H H H H H H H H H hartree kcal/mol kj/mol Total Charge: 0.00 Spin Polarisation: 2.00 change in energy gradient max gradient rms Electrostatic Energy: Kinetic Energy: Coulomb (Steric+OrbInt) Energy: XC Energy: Solvation:
9 ENERGIES AND CARTESIAN COORDINATES OF THE MODEL SYSTEM [{Mn(dHpe) 2 I} 2 (m-c 4 )] + Mn P P C I P P C Mn P P P P I C C C H H C H H C H H C H H C H H C H H C H H C H H H H H H H H H H H H H H H H H H hartree kcal/mol kj/mol Total Charge: 1.00 Spin Polarisation: 1.00 change in energy gradient max gradient rms Electrostatic Energy: Kinetic Energy: Coulomb (Steric+OrbInt) Energy: XC Energy: Solvation: ENERGIES AND CARTESIAN COORDINATES OF THE MODEL SYSTEM [{Mn(dHpe) 2 I} 2 (m-c 4 )] 2+
10 Mn P P C I P P C Mn P P P P I C C C H H C H H C H H C H H C H H C H H C H H C H H H H H H H H H H H H H H H H H H
11 hartree kcal/mol kj/mol Total Charge: 2.00 change in energy gradient max gradient rms Electrostatic Energy: Kinetic Energy: Coulomb (Steric+OrbInt) Energy: XC Energy: Solvation: Experimental Data c m T (emu K mol -1 ) T (K) Figure 1. Temperature dependance of the molar magnetic susceptibility χ m for compound 11.
12 UV/VIS/NIR spectra of [{H-C C-Mn(dmpe) 2 } 2 (µ-c4)] n+ n = 0 n = 1 n = e (M -1 cm -1 ) l (nm) Figure 2. UV/visible spectra of 11, [11] + and [11] 2+ (CH 2 Cl 2, ambient temperature, M) c m T (emu K mol -1 ) T (K) Figure 3. Temperature dependance of the molar magnetic susceptibility χ m for compound [11] +.
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