204923-08-0Relevant articles and documents
Efficient Self-Assembly of Di-, Tri-, Tetra-, and Hexavalent Hosts with Predefined Geometries for the Investigation of Multivalency
Linder, Igor,Leisering, Stefan,Puttreddy, Rakesh,Rades, Nadine,Rissanen, Kari,Schalley, Christoph A.
, p. 13035 - 13044 (2015)
Coordination-driven self-assembly of differently shaped di- to hexavalent crown-ether host molecules is described. A series of [21]crown-7- and [24]crown-8-substituted bipyridine and terpyridine ligands was synthetized in a "toolbox" approach. Subsequent
Fine-Tuning Metal and Ligand-Centered Redox Potentials of Homoleptic Bis-Terpyridine Complexes with 4′-Aryl Substituents
Dickenson, John C.,Haley, Mackenzie E.,Hyde, Jacob T.,Reid, Zachary M.,Tarring, Travis J.,Iovan, Diana A.,Harrison, Daniel P.
, p. 9956 - 9969 (2021/07/19)
Homoleptic transition-metal complexes of 2,2':6′,2″-terpyridine (terpy) and substituted derivatives of the form [M(R-terpy)2]2+ display a wide range of redox potentials that correlate well to the Hammett parameter of the terpy substituents. Less is known about the impact of incorporating a phenyl spacer between the functional group responsible for controlling the electron density of terpy and how that translates to metal complexes of the form [M(4′-aryl-terpy)2]2+, where M = Mn, Fe, Co, Ni, and Zn. Herein, we report our studies on these complexes revealed a good correlation of redox potentials of both metal- and ligand-centered events with the Hammett parameters of the aryl substituents, regardless of aryl-substitution pattern (i.e., the presence of multiple functional groups, combinations of withdrawing and donating functional groups). The phenyl spacer results in 60-80% attenuation of electron density as compared to the 4′-substituted terpy analogue, depending on the metal and redox couple analyzed. Density functional theory calculations performed on a simple model system revealed a strong correlation between the Hammett parameters and lowest unoccupied molecular orbital energies of the corresponding substituted pyridine models, thus serving as an inexpensive predictive tool when coupled with electrochemical data. Overall, these data suggest that such ligand modifications may be used in combination with previous approaches to further fine-tune the redox potentials of homoleptic transition-metal complexes, which may have applications in photochemical and electrochemical catalytic processes.
Self-Healing Heterometallic Supramolecular Polymers Constructed by Hierarchical Assembly of Triply Orthogonal Interactions with Tunable Photophysical Properties
Zhang, Qian,Tang, Danting,Zhang, Jinjin,Ni, Ruidong,Xu, Luonan,He, Tian,Lin, Xiongjie,Li, Xiaopeng,Qiu, Huayu,Yin, Shouchun,Stang, Peter J.
supporting information, p. 17909 - 17917 (2019/11/11)
Here, we present a method for the building of new bicyclic heterometallic cross-linked supramolecular polymers by hierarchical unification of three types of orthogonal noncovalent interactions, including platinum(II)-pyridine coordination-driven self-asse
A redox asymmetric, cyclometalated ruthenium dimer: Toward upconversion dyes in dye-sensitized TiO2 solar cells
Wadman, Sipke H.,Van Leeuwen,Havenith, Remco W. A.,Van Klink, Gerard P. M.,Van Koten, Gerard
experimental part, p. 5635 - 5645 (2011/01/03)
We have prepared the dinuclear ruthenium complexes [(R3-tpy) Ru(N^C^N-tpy)Ru(tpy)]3+ (R = H ([5a]3+), CO2Me ([6a]3+), N^C(H)^N-tpy = 4′-(3,5-dipyridylphenyl)-2,2′: 6′,2″-terpyridine, tpy = 2,2′:6′,2″-terpyridine) and [(R3-tpy)Ru(N′^C^N′-tpy)Ru(tpy)]3+ (R = H ([5b]3+), CO2Me ([6b]3+), N′^C(H) ^N′-tpy = 4′-(3,5-di(4-tert-butylpyridyl)phenyl)-2,2′: 6′,2″-terpyridine) in a stepwise manner. The directional nature of the bridging ligand, which is potentially cyclometalating on one side, induces large redox asymmetry in the resulting dinuclear complexes. One-electron oxidation gives rise to a strong metal-to-metal charge transfer transition from the [Ru(tpy2)]2+ moiety to the cycloruthenated group, centered at 1034 nm for [6b]4+. The localized nature of the oxidation processes, the shape of the NIR band, and TD-DFT calculations allow assignment of these systems to localized Robin-Day class II. Exclusive substitution of the terminal tpy ligand on the cyclometalated ruthenium with acid moieties allows selective attachment of the dye to a semiconductor surface, whereby a possible two-step upconversion path is created in dye-sensitized solar cells for the utilization of low-energy photons.
Long-range electronic coupling in bis(cyclometalated) ruthenium complexes
Patoux, Cendrine,Launay, Jean-Pierre,Beley, Marc,Chodorowski-Kimmes, Sandrine,Collin, Jean-Paul,James, Stuart,Sauvage, Jean-Pierre
, p. 3717 - 3725 (2007/10/03)
Symmetrical and unsymmetrical ligands containing terpyridyl coordinating units (N, N, N) or a cyclometalating equivalent (N, C, N), connected back- to-back either directly or via a p-terphenylene or 1,3-phenylene spacer, have been used to construct new di
