Synthesis, luminescence, and electrochemical studies of a new series of octanuclear ruthenium(ii) complexes of tolylterpyridine appended calixresorcarenesElectronic supplementary information (ESI) available: Crystallographic data in CIF format, relevant absorption, emission, and excitation spectra of free ligands and complexes, cyclic voltammograms of complexes, mass and NMR spectra of all organic precursors, and free ligands, and mass spectra of complexes. CCDC 812939 (1), 836167 (2) and 847907

A new series of octanuclear Ru( ii ) complexes of tolylterpyridine appended calixresorcarenes [{Ru(ttpy)} 8 ( L1 )](PF 6 ) 16 ( 4 ), [{Ru(ttpy)} 8 ( L2 )](PF 6 ) 16 ( 5 ), and [{Ru(ttpy)} 8 ( L3 )](PF 6 ) 16 ( 6 ) [ L1 = 2,8,14,20-tetraethyl-4,6,10,12,16,18,22,24-octa(4′- p -benzyloxy-(2,2′:6′,2′′-terpyridinyl))calix[4]resorcarene; L2 = 2,8,14,20-tetraphenyl-4,6,10,12,16,18,22,24-octa(4′- p -benzyloxy-(2,2′:6′,2′′-terpyridinyl))calix[4]resorcarene; and L3 = 2,8,14,20-tetra- p -tolyl-4,6,10,12,16,18,22,24-octa(4′- p -benzyloxy-(2,2′:6′,2′′-terpyridinyl))calix[4]resorcarene] have been synthesized and characterized. The tetraethyl-, tetraphenyl-, and tetra- p -tolylcalixresorcarenes ( 1 ), ( 2 ), and ( 3 ), respectively, are characterized by single crystal X-ray diffraction: ( 1 ) a = 13.5771(4) Å, b = 7.9566(3) Å, c = 18.3912(6) Å, α = γ = 90°, β = 103.146(2)°, V = 1934.69(11) Å 3 , Z = 2, monoclinic, P 2/ n ; ( 2 ) a = 11.9710(8) Å, b = 12.7057(9) Å, c = 13.8570(9) Å, α = 94.731(2)°, β = 108.558(2)°, γ = 106.657(2)°, V = 1878.9(2) Å 3 , Z = 1, triclinic, P 1&cmb.macr;; and ( 3 ) a = 26.076(3) Å, b = 20.056(2) Å, c = 16.0193(19) Å, α = γ = 90°, β = 116.056(3)°, V = 7526.3(14) Å 3 , Z = 4, monoclinic, C 2/ c , respectively. The octanuclear complexes 4-6 are nonluminescent at 298 K, but exhibit 3 MLCT luminescence at 654, 649, and 646 nm, respectively, at 77 K in acetonitrile. In the solid state at 298 K they exhibit 3 MLCT luminescence at 658, 658, and 665 nm, respectively. The complexes exhibit a monoexponential decay profile in acetonitrile and in the solid state at 298 K. The redox active hosts 4-6 containing eight [Ru(ttpy) 2 ] 2+ moieties undergo quasireversible one-electron oxidation at 1.25, 1.26, and 1.25 V versus Ag/Ag + , respectively, in acetonitrile. The study demonstrates the versatility of the octanucleating calixresorcarene based ligands L1 , L2 , and L3 in forming octanuclear Ru( ii ) complexes. A series of octanuclear ruthenium( ii ) complexes of tolylterpyridine appended calixresorcarenes were synthesized and their luminescence and electrochemical properties were investigated.