(8-Amino)quinoline and (4-amino)phenanthridine complexes of Re(CO)3 halides

Platinum(ii) complexes of benzannulated N∧N−∧O-amido ligands: bright orange phosphors with long-lived excited states

“…Previous computational modelling on the UV-Vis absorption spectra of Re(I) carbonyl complexes supported by 8-aminophenanthridines and 4-aminoquinolines indicated that SOC is necessary in accounting for a weak, low-energy transition in the 450-650 nm range of such complexes. 45 In addition, an increasing body of literature supports the necessity of SOC to properly model the absorption spectra of complexes containing heavy elements, providing a mechanism to the direct population of low-lying excited triplet states. [45][46][47][48] SOC-TDDFT simulated spectra for all four complexes calculated using a polarizable continuum of CH 2 Cl 2 are in excellent agreement with the experimental UV-Vis absorption spectra (Figures S10-S13, Tables S9-S12).…”

“…45 In addition, an increasing body of literature supports the necessity of SOC to properly model the absorption spectra of complexes containing heavy elements, providing a mechanism to the direct population of low-lying excited triplet states. [45][46][47][48] SOC-TDDFT simulated spectra for all four complexes calculated using a polarizable continuum of CH 2 Cl 2 are in excellent agreement with the experimental UV-Vis absorption spectra (Figures S10-S13, Tables S9-S12). In general, our simulations suggest that two important transitions (f osc > 0.003) are responsible for the lowest energy manifold of the experimental UV-Vis spectra.…”

Donor–Acceptor Boron-Ketoiminate Complexes with Pendent N-Heterocyclic Arms: Switched-on Luminescence through N-Heterocycle Methylation

“…The phenanthridinyl substituents do not appear to impact the calculated HOMO–LUMO gaps, mirroring the similarity in λ abs,max for 1 – 4 , while the bathochromic shift to the lowest energy manifold of [ 3 Me] + compared to 3 is reproduced by computation. As with coordination complexes of Lewis acidic metal ions supported by phenanthridine-based ligand scaffolds, − the LUMO has particularly localized orbital density at the CN subunit of the phenanthridinyl, consistent with “imine-bridged biphenyl” character to the tricyclic moiety. This is accentuated upon methylation of the phenanthridinyl nitrogen, such that the LUMO of 3 has 70% phenanthridine character, 21% of which is localized at the CN subunit, while the comparable numbers for [ 3 Me] + are 94% and 38%.…”

When is a pyridine not a pyridine? Benzannulated N-heterocyclic ligands in molecular materials chemistry

“…We generally access these via a one-pot, tandem Pd-catalyzed cross-coupling/condensation protocol between appropriately substituted anilines and 2-formylphenyl boronic acid derivatives. 35 From 4-bromo/4-amino phenanthridines, we can then construct P^N 35 , N^N 36,37 , N^N^N 38,39 , N^N^O [40][41][42] , N^C^N 43 and N^N^P 44 proligands; C^N and 8 bpy-style (N^N) 2 biphenanthridine 45 proligands are available from (6-halo)phenanthridines. 46 Coordination complexes of these ligands can be used in the Ni-catalyzed direct alkylation of C-H bonds in azoles, 39 as well as to effect acceptorless dehydrogenative coupling reactions in which alcohols can be employed as electrophiles.…”