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The bottom‐up functionalization of solid surfaces shows increasing importance for a wide range of interdisciplinary applications. Multidentate anchors with more than two contact points can bind to solid surfaces with strong chemisorption, well‐defined upright configuration, and tailored functionality. The surface functionalization using multidentate anchors with three (tripodal), four (quadripodal), or more binding points is summarized herein, with a focus on those beyond classical tripodal anchors. In particular, the molecular design on how to achieve multisite interaction between anchor and substrate and the introduction of functional groups to thin films are discussed. [ABSTRACT FROM AUTHOR]

Four heterodimetallic complexes [Ru(Fcdpb)(L)](PF6) (Fcdpb=2-deprotonated form of 1,3-di(2-pyridyl)-5-ferrocenylbenzene; L=2,6-bis-( N-methylbenzimidazolyl)-pyridine (Mebip), 2,2′:6′,2′′-terpyridine (tpy), 4-nitro-2,2′:6′,2′′-terpyridine (NO2tpy), and trimethyl-4,4′,4′′-tricarboxylate-2,2′:6′,2′′-terpyridine (Me3tctpy)) have been prepared. The electrochemical and spectroelectrochemical properties of these complexes have been examined in CH2Cl2, CH3NO2, CH3CN, and acetone. These complexes display two consecutive redox couples owing to the stepwise oxidation of the ferrocene (Fc) and ruthenium units, respectively. The potential difference, Δ E1/2 ( E1/2(RuII/III)− E1/2(Fc0/+)), decreased slightly with increasing solvent donocity. The mixed-valent states of these complexes have been generated by and the resulting intervalence charge-transfer (IVCT) bands have been analyzed by Hush theory. Good linear relationships exist between the energy of the IVCT band, Eop, and Δ E1/2 of four mixed-valent complexes in a given solvent. [ABSTRACT FROM AUTHOR]

A new bridging ligand, 2,3-di(2-pyridyl)-5-phenylpyrazine (dpppzH), has been synthesized. This ligand was designed so that it could bind two metals through a NN-CNN-type coordination mode. The reaction of dpppzH with cis-[(bpy)2RuCl2] (bpy=2,2′-bipyridine) affords monoruthenium complex [(bpy)2Ru(dpppzH)]2+ ( 12+) in 64 % yield, in which dpppzH behaves as a NN bidentate ligand. The asymmetric biruthenium complex [(bpy)2Ru(dpppz)Ru(Mebip)]3+ ( 23+) was prepared from complex 12+ and [(Mebip)RuCl3] (Mebip=bis( N-methylbenzimidazolyl)pyridine), in which one hydrogen atom on the phenyl ring of dpppzH is lost and the bridging ligand binds to the second ruthenium atom in a CNN tridentate fashion. In addition, the RuPt heterobimetallic complex [(bpy)2Ru(dpppz)Pt(CCPh)]2+ ( 42+) has been prepared from complex 12+, in which the bridging ligand binds to the platinum atom through a CNN binding mode. The electronic properties of these complexes have been probed by using electrochemical and spectroscopic techniques and studied by theoretical calculations. Complex 12+ is emissive at room temperature, with an emission λmax=695 nm. No emission was detected for complex 23+ at room temperature in MeCN, whereas complex 42+ displayed an emission at about 750 nm. The emission properties of these complexes are compared to those of previously reported Ru and RuPt bimetallic complexes with a related ligand, 2,3-di(2-pyridyl)-5,6-diphenylpyrazine. [ABSTRACT FROM AUTHOR]

Three bis-tridentate ferrocene-containing cyclometalated ruthenium complexes, [(Fcdpb)Ru(tpy)]+ ( 1+), [(Fctpy)Ru(dpb)]+ ( 2+), and [(Fcdpb)Ru(Fctpy)]+ ( 3+), have been prepared and characterized, where Fcdpb is the 2-deprotonated form of 1,3-di(2-pyridyl)-5-ferrocenylbenzene, tpy is 2,2′:6′,2'-terpyridine, dpb is the 2-deprotonated form of 1,3-di(2-pyridyl)benzene, and Fctpy is 4′-ferrocenyl-2,2′:6′,2'-terpyridine. Single crystals of compounds 2+ and 3+ have been studied by X-ray analysis. Complexes 1+ and 2+ displayed two anodic redox waves, whilst three well-separated redox couples were observed for compound 3+. A combined experimental and computational study suggested that the ferrocene unit on the Fcdpb moiety in compounds 1+ and 3+ was oxidized first. In contrast, the order of the oxidation of ruthenium and ferrocene in complex 2+ was reversed. Metal-to-metal-charge-transfer transitions (MM′CT) have been observed for the singly oxidized states 12+, 22+, and 32+ in the near-infrared region. Hush analysis showed that the metal-metal electronic couplings in compounds 12+ and 32+ were much stronger than those in compound 22+. [ABSTRACT FROM AUTHOR]