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1.
Aaron Breivogel Michael Meister Dr. Christoph Förster Dr. Frédéric Laquai Prof. Dr. Katja Heinze 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(41):13745-13760
The synergy of push–pull substitution and enlarged ligand bite angles has been used in functionalized heteroleptic bis(tridentate) polypyridine complexes of ruthenium(II) to shift the 1MLCT absorption and the 3MLCT emission to lower energy, enhance the emission quantum yield, and to prolong the 3MLCT excited‐state lifetime. In these complexes, that is, [Ru(ddpd)(EtOOC‐tpy)][PF6]2, [Ru(ddpd‐NH2)(EtOOC‐tpy)][PF6]2, [Ru(ddpd){(MeOOC)3‐tpy}][PF6]2, and [Ru(ddpd‐NH2){(EtOOC)3‐tpy}][PF6]2 the combination of the electron‐accepting 2,2′;6′,2′′‐terpyridine (tpy) ligand equipped with one or three COOR substituents with the electron‐donating N,N′‐dimethyl‐N,N′‐dipyridin‐2‐ylpyridine‐2,6‐diamine (ddpd) ligand decorated with none or one NH2 group enforces spatially separated and orthogonal frontier orbitals with a small HOMO–LUMO gap resulting in low‐energy 1MLCT and 3MLCT states. The extended bite angle of the ddpd ligand increases the ligand field splitting and pushes the deactivating 3MC state to higher energy. The properties of the new isomerically pure mixed ligand complexes have been studied by using electrochemistry, UV/Vis absorption spectroscopy, static and time‐resolved luminescence spectroscopy, and transient absorption spectroscopy. The experimental data were rationalized by using density functional calculations on differently charged species (charge n=0–4) and on triplet excited states (3MLCT and 3MC) as well as by time‐dependent density functional calculations (excited singlet states). 相似文献
2.
(Oligopyridine)ruthenium(II) complexes have been widely used in dye sensitized solar cells and other sophisticated optical devices due to their outstanding photophysical properties and their chemical stability. Herein, we describe the longitudinal extension of our previously reported bis(terpyridine)ruthenium(II) amino acid [Ru(tpy–NH2)(tpy–COOH)]2+ (tpy = 4′‐substituted 2,2′:6′,2″‐terpyridine) by insertion of para‐phenylene spacers –C6H4– between the terpyridine and the functional groups. The influence of the para‐phenylene spacer on the absorption and emission properties is investigated using UV/Vis absorption and emission spectroscopy and is discussed within a qualitative molecular orbital picture. 相似文献
3.
Si‐Hai Wu Jiang‐Yang Shao Hong‐Wei Kang Prof. Dr. Jiannian Yao Prof. Dr. Yu‐Wu Zhong 《化学:亚洲杂志》2013,8(11):2843-2850
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, ΔE1/2 (E1/2(RuII/III)?E1/2(Fc0/+)), decreased slightly with increasing solvent donocity. The mixed‐valent states of these complexes have been generated by electrolysis 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 ΔE1/2 of four mixed‐valent complexes in a given solvent. 相似文献
4.
Dr. Ana Conde Dr. Rosa Fandos Dr. Carolina Hernández Prof. Dr. Antonio Otero Dr. Ana Rodríguez Dr. María José Ruiz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(8):2319-2326
Tantalum complexes [TaCp*Me{κ4‐C,N,O,O‐(OCH2)(OCHC(CH2NMe2)?CH)py}] ( 4 ) and [TaCp*Me{κ4‐C,N,O,O‐(OCH2)(OCHC(CH2NH2)?CH)py}] ( 5 ), which contain modified alkoxide pincer ligands, were synthesized from the reactions of [TaCp*Me{κ3‐N,O,O‐(OCH2)(OCH)py}] (Cp*=η5‐C5Me5) with HC?CCH2NMe2 and HC?CCH2NH2, respectively. The reactions of [TaCp*Me{κ4‐C,N,O,O‐(OCH2)(OCHC(Ph)?CH)py}] ( 2 ) and [TaCp*Me{κ4‐C,N,O,O‐(OCH2)(OCHC(SiMe3)?CH)py}] ( 3 ) with triflic acid (1:2 molar ratio) rendered the corresponding bis‐triflate derivatives [TaCp*(OTf)2{κ3‐N,O,O‐(OCH2)(OCHC(Ph)?CH2)py}] ( 6 ) and [TaCp*(OTf)2{κ3‐N,O,O‐(OCH2)(OCHC(SiMe3)?CH2)py}] ( 7 ), respectively. Complex 4 reacted with triflic acid in a 1:2 molar ratio to selectively yield the water‐soluble cationic complex [TaCp*(OTf){κ4‐C,N,O,O‐(OCH2)(OCHC(CH2NHMe2)?CH)py}]OTf ( 8 ). Compound 8 reacted with water to afford the hydrolyzed complex [TaCp*(OH)(H2O){κ3‐N,O,O‐(OCH2)(OCHC(CH2NHMe2)?CH2)py}](OTf)2 ( 9 ). Protonation of compound 8 with triflic acid gave the new tantalum compound [TaCp*(OTf){κ4‐C,N,O,O‐(OCH2)(HOCHC(CH2NHMe2)?CH)py}](OTf)2 ( 10 ), which afforded the corresponding protonolysis derivative [TaCp*(OTf)2{κ3‐N,O,O‐(OCH2)(HOCHC(CH2NHMe2)?CH2)py}](OTf) ( 11 ) in solution. Complex 8 reacted with CNtBu and potassium 2‐isocyanoacetate to give the corresponding iminoacyl derivatives 12 and 13 , respectively. The molecular structures of complexes 5 , 7 , and 10 were established by single‐crystal X‐ray diffraction studies. 相似文献
5.
Deeb Taher Prof. Dr. Michelle E. Thibault Domenico Di Mondo Michael Jennings Marcel Schlaf Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(39):10132-10143
The ruthenium aqua complexes [Ru(H2O)2(bipy)2](OTf)2, [cis‐Ru(6,6′‐Cl2‐bipy)2(OH2)2](OTf)2, [Ru(H2O)2(phen)2](OTf)2, [Ru(H2O)3(2,2′:6′,2′′‐terpy)](OTf)2 and [Ru(H2O)3(Phterpy)](OTf)2 (bipy=2,2′‐bipyridine; OTf?=triflate; phen=phenanthroline; terpy= terpyridine; Phterpy=4′‐phenyl‐2,2′:6′,2′′‐terpyridine) are water‐ and acid‐stable catalysts for the hydrogenation of aldehydes and ketones in sulfolane solution. In the presence of HOS(O)2CF3 (triflic acid) as a dehydration co‐catalyst they directly convert 1,2‐hexanediol to n‐hexanol and hexane. The terpyridine complexes are stable and active as catalysts at temperatures ≥250 °C and in either aqueous sulfolane solution or pure water convert glycerol into n‐propanol and ultimately propane as the final reaction product in up to quantitative yield. For the terpy complexes the active catalyst is postulated to be a carbonyl species [(4′‐R‐2,2′:6′,2′′‐terpy)Ru(CO)(H2O)2](OTf)2 (R=H, Ph) formed by the decarbonylation of aldehydes (hexanal for 1,2‐hexanediol and 3‐hydroxypropanal for glycerol) generated in the reaction mixture through acid‐catalyzed dehydration. The structure of the dimeric complex [{(4′‐phenyl‐2,2′:6′,2′′‐terpy)Ru(CO)}2(μ‐OCH3)2](OTf)2 has been determined by single crystal X‐ray crystallography (Space group P (a=8.2532(17); b=12.858(3); c=14.363(3) Å; α=64.38(3); β=77.26(3); γ = 87.12(3)°, R=4.36 %). 相似文献
6.
Juan Granifo Rubn Gavio Eleonora Freire Ricardo Baggio 《Acta Crystallographica. Section C, Structural Chemistry》2012,68(10):m269-m274
The Zn complexes bis(acetylacetonato‐κ2O,O′)bis{4′‐[4‐(methylsulfanyl)phenyl]‐4,2′:6′,4′′‐terpyridine‐κN1}zinc(II), [Zn(C5H7O2)2(C22H17N3S)2], (I), and {μ‐4′‐[4‐(methylsulfanyl)phenyl]‐4,2′:6′,4′′‐terpyridine‐κ2N1:N1′′}bis[bis(acetylacetonato‐κ2O,O′)zinc(II)], [Zn2(C5H7O2)4(C22H17N3S)], (II), are discrete entities with different nuclearities. Compound (I) consists of two centrosymmetrically related monodentate 4′‐[4‐(methylsulfanyl)phenyl]‐4,2′:6′,4′′‐terpyridine (L1) ligands binding to one ZnII atom sitting on an inversion centre and two centrosymmetrically related chelating acetylacetonate (acac) groups which bind via carbonyl O‐atom donors, giving an N2O4 octahedral environment for ZnII. Compound (II), however, consists of a bis‐monodentate L1 ligand bridging two ZnII atoms from two different Zn(acac)2 fragments. Intra‐ and intermolecular interactions are weak, mainly of the C—H...π and π–π types, mediating similar layered structures. In contrast to related structures in the literature, sulfur‐mediated nonbonding interactions in (II) do not seem to have any significant influence on the supramolecular structure. 相似文献
7.
Judicious Ligand Design in Ruthenium Polypyridyl CO2 Reduction Catalysts to Enhance Reactivity by Steric and Electronic Effects
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Ben A. Johnson Dr. Hemlata Agarwala Dr. Travis A. White Dr. Edgar Mijangos Prof. Dr. Somnath Maji Prof. Dr. Sascha Ott 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(42):14870-14880
A series of RuII polypyridyl complexes of the structural design [RuII(R?tpy)(NN)(CH3CN)]2+ (R?tpy=2,2′:6′,2′′‐terpyridine (R=H) or 4,4′,4′′‐tri‐tert‐butyl‐2,2′:6′,2′′‐terpyridine (R=tBu); NN=2,2′‐bipyridine with methyl substituents in various positions) have been synthesized and analyzed for their ability to function as electrocatalysts for the reduction of CO2 to CO. Detailed electrochemical analyses establish how substitutions at different ring positions of the bipyridine and terpyridine ligands can have profound electronic and, even more importantly, steric effects that determine the complexes’ reactivities. Whereas electron‐donating groups para to the heteroatoms exhibit the expected electronic effect, with an increase in turnover frequencies at increased overpotential, the introduction of a methyl group at the ortho position of NN imposes drastic steric effects. Two complexes, [RuII(tpy)(6‐mbpy)(CH3CN)]2+ (trans‐[ 3 ]2+; 6‐mbpy=6‐methyl‐2,2′‐bipyridine) and [RuII(tBu?tpy)(6‐mbpy)(CH3CN)]2+ (trans‐[ 4 ]2+), in which the methyl group of the 6‐mbpy ligand is trans to the CH3CN ligand, show electrocatalytic CO2 reduction at a previously unreactive oxidation state of the complex. This low overpotential pathway follows an ECE mechanism (electron transfer–chemical reaction–electron transfer), and is a direct result of steric interactions that facilitate CH3CN ligand dissociation, CO2 coordination, and ultimately catalytic turnover at the first reduction potential of the complexes. All experimental observations are rigorously corroborated by DFT calculations. 相似文献
8.
Chang‐Jiang Yao Dr. Ren‐Hui Zheng Hai‐Jing Nie Bin‐Bin Cui Prof. Dr. Qiang Shi Prof. Dr. Jiannian Yao Prof. Dr. Yu‐Wu Zhong 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(37):12376-12387
Two series of linear ruthenium coordination oligomers, [(Ntpy)Run(tppz)n?1(tpy)]2n+ (mono‐Ntpy series, n=1–3) and [(Ntpy)2Run(tppz)n?1]2n+ (bis‐Ntpy series, n=1–3) have been prepared, where Ntpy is the capping ligand 4′‐di‐p‐anisylamino‐2,2′:6′,2′′‐terpyridine, tppz is tetra‐2‐pyridylpyrazine, and tpy is 2,2′:6′,2′′‐terpyridine. The electrochemical measurements evidence oxidation events from both the amine segments and the metal centers and reduction waves from tppz and the capping ligands. Both series complexes display much enhanced light absorption with respect to model complexes without terminal amine units. Density functional theory (DFT) calculations have been performed on both series and time‐dependent DFT (TD‐DFT) calculations have been performed on the bis‐Ntpy‐series compounds (n=1–4) to characterize their electronic structures and excited states and predict the electronic properties of long‐chain polymers. Upon one‐electron oxidation, the mono‐Ntpy‐series monoruthenium and diruthenium complexes display N+‐localized transitions and metal‐to‐nitrogen charge‐transfer (MNCT) transitions in the near‐infrared (NIR) region. DFT and TD‐DFT computations on the one‐electron‐oxidized forms of the mono‐Ntpy‐series compounds (n=1–4) provide insight into the nature of the MNCT transitions and the degree of charge delocalization. 相似文献
9.
A Cytostatic Ruthenium(II)–Platinum(II) Bis(terpyridyl) Anticancer Complex That Blocks Entry into S Phase by Up‐regulating p27KIP1
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Vadde Ramu Dr. Martin R. Gill Paul J. Jarman Dr. David Turton Prof. Jim A. Thomas Dr. Amitava Das Prof. Carl Smythe 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(25):9185-9197
Cytostatic agents that interfere with specific cellular components to prevent cancer cell growth offer an attractive alternative, or complement, to traditional cytotoxic chemotherapy. Here, we describe the synthesis and characterization of a new binuclear RuII–PtII complex [Ru(tpy)(tpypma)Pt(Cl)(DMSO)]3+ (tpy=2,2′:6′,2′′‐terpyridine and tpypma=4‐([2,2′:6′,2′′‐terpyridine]‐4′‐yl)‐N‐(pyridin‐2‐ylmethyl)aniline), VR54, which employs the extended terpyridine tpypma ligand to link the two metal centres. In cell‐free conditions, VR54 binds DNA by non‐intercalative reversible mechanisms (Kb=1.3×105 M ?1) and does not irreversibly bind guanosine. Cellular studies reveal that VR54 suppresses proliferation of A2780 ovarian cancer cells with no cross‐resistance in the A2780CIS cisplatin‐resistant cell line. Through the preparation of mononuclear RuII and PtII structural derivatives it was determined that both metal centres are required for this anti‐proliferative activity. In stark contrast to cisplatin, VR54 neither activates the DNA‐damage response network nor induces significant levels of cell death. Instead, VR54 is cytostatic and inhibits cell proliferation by up‐regulating the cyclin‐dependent kinase inhibitor p27KIP1 and inhibiting retinoblastoma protein phosphorylation, which blocks entry into S phase and results in G1 cell cycle arrest. Thus, VR54 inhibits cancer cell growth by a gain of function at the G1 restriction point. This is the first metal‐coordination compound to demonstrate such activity. 相似文献
10.
《无机化学与普通化学杂志》2018,644(18):1115-1122
A metal‐containing N‐heterocyclic germylene based on a N‐mesityl (Mes)‐substituted oxalamidine framework is reported. The precursor (MesN=)2C–C(–N(H)Mes)2 ( 1 H2) was converted into its rhodium complex [Rh(κ2N‐ 1 H2)(cod)][OTf] ( 2 ) (cod = 1,5‐cyclooctadiene; OTf = triflate) in 62 % isolated yield. Subsequent reaction of 2 with Ge{N(SiMe3)2}2 gave the crystalline N‐heterocyclic germylene [Rh(cod)(μ‐ 1 )Ge][OTf] ( 3 ) in 50 % yield. The compounds under study were fully characterized by various methods, also including X‐ray crystallographic studies on single crystals of 2 and 3 . Density functional theory (DFT) calculations revealed that π conjugation in the bridging oxalamidine framework is increased and n(N)–p(Ge) π bonding is decreased upon κ2N metal coordination; a further weakening of the Ge–N bond occurs through triflate coordination to the GeII atom. Nevertheless, preliminary coordination studies revealed that 3 behaves as 2‐electron (L ‐type) germylene donor ligand. Treatment of 3 with [Ir(cod)Cl]2 furnished the heterobimetallic complex [Rh(cod)(μ‐ 1 )Ge‐Ir(cod)Cl][OTf] ( 4 ), as evidenced by NMR spectroscopic investigations and DFT calculations. 相似文献
11.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(35):10631-10636
Reaction of [U(TrenTIPS)(PH2)] ( 1 , TrenTIPS=N(CH2CH2NSiPri3)3) with C6H5CH2K and [U(TrenTIPS)(THF)][BPh4] ( 2 ) afforded a rare diuranium parent phosphinidiide complex [{U(TrenTIPS)}2(μ‐PH)] ( 3 ). Treatment of 3 with C6H5CH2K and two equivalents of benzo‐15‐crown‐5 ether (B15C5) gave the diuranium μ‐phosphido complex [{U(TrenTIPS)}2(μ‐P)][K(B15C5)2] ( 4 ). Alternatively, reaction of [U(TrenTIPS)(PH)][Na(12C4)2] ( 5 , 12C4=12‐crown‐4 ether) with [U{N(CH2CH2NSiMe2But)2CH2CH2NSi(Me)(CH2)(But)}] ( 6 ) produced the diuranium μ‐phosphido complex [{U(TrenTIPS)}(μ‐P){U(TrenDMBS)}][Na(12C4)2] [ 7 , TrenDMBS=N(CH2CH2NSiMe2But)3]. Compounds 4 and 7 are unprecedented examples of uranium phosphido complexes outside of matrix isolation studies, and they rapidly decompose in solution underscoring the paucity of uranium phosphido complexes. Interestingly, 4 and 7 feature symmetric and asymmetric UPU cores, respectively, reflecting their differing steric profiles. 相似文献
12.
Glenna So Ming Tong Dr. Yuen‐Chi Law Dr. Steven C. F. Kui Dr. Nianyong Zhu Dr. King Hong Leung Dr. David Lee Phillips Prof. Chi‐Ming Che Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(22):6540-6554
The complexes [Pt(tBu3tpy){C?C(C6H4C?C)n?1R}]+ (n=1: R=alkyl and aryl (Ar); n=1–3: R=phenyl (Ph) or Ph‐N(CH3)2‐4; n=1 and 2, R=Ph‐NH2‐4; tBu3tpy=4,4’,4’’‐tri‐tert‐butyl‐2,2’:6’,2’’‐terpyridine) and [Pt(Cl3tpy)(C?CR)]+ (R=tert‐butyl (tBu), Ph, 9,9’‐dibutylfluorene, 9,9’‐dibutyl‐7‐dimethyl‐amine‐fluorene; Cl3tpy=4,4’,4’’‐trichloro‐2,2’:6’,2’’‐terpyridine) were prepared. The effects of substituent(s) on the terpyridine (tpy) and acetylide ligands and chain length of arylacetylide ligands on the absorption and emission spectra were examined. Resonance Raman (RR) spectra of [Pt(tBu3tpy)(C?CR)]+ (R=n‐butyl, Ph, and C6H4‐OCH3‐4) obtained in acetonitrile at 298 K reveal that the structural distortion of the C?C bond in the electronic excited state obtained by 502.9 nm excitation is substantially larger than that obtained by 416 nm excitation. Density functional theory (DFT) and time‐dependent DFT (TDDFT) calculations on [Pt(H3tpy)(C?CR)]+ (R= n‐propyl (nPr), 2‐pyridyl (Py)), [Pt(H3tpy){C?C(C6H4C?C)n?1Ph}]+ (n=1–3), and [Pt(H3tpy){C?C(C6H4C?C)n?1C6H4‐N(CH3)2‐4}]+/+H+ (n=1–3; H3tpy=nonsubstituted terpyridine) at two different conformations were performed, namely, with the phenyl rings of the arylacetylide ligands coplanar (“cop”) with and perpendicular (“per”) to the H3tpy ligand. Combining the experimental data and calculated results, the two lowest energy absorption peak maxima, λ1 and λ2, of [Pt(Y3tpy)(C?CR)]+ (Y=tBu or Cl, R=aryl) are attributed to 1[π(C?CR)→π*(Y3tpy)] in the “cop” conformation and mixed 1[dπ(Pt)→π*(Y3tpy)]/1[π(C?CR)→π*(Y3tpy)] transitions in the “per” conformation. The lowest energy absorption peak λ1 for [Pt(tBu3tpy){C?C(C6H4C?C)n?1C6H4‐H‐4}]+ (n=1–3) shows a redshift with increasing chain length. However, for [Pt(tBu3tpy){C?C(C6H4C?C)n?1C6H4‐N(CH3)2‐4}]+ (n=1–3), λ1 shows a blueshift with increasing chain length n, but shows a redshift after the addition of acid. The emissions of [Pt(Y3tpy)(C?CR)]+ (Y=tBu or Cl) at 524–642 nm measured in dichloromethane at 298 K are assigned to the 3[π(C?CAr)→π*(Y3tpy)] excited states and mixed 3[dπ(Pt)→π*(Y3tpy)]/3[π(C?C)→π*(Y3tpy)] excited states for R=aryl and alkyl groups, respectively. [Pt(tBu3tpy){C?C(C6H4C?C)n?1C6H4‐N(CH3)2‐4}]+ (n=1 and 2) are nonemissive, and this is attributed to the small energy gap between the singlet ground state (S0) and the lowest triplet excited state (T1). 相似文献
13.
Activating a Low Overpotential CO2 Reduction Mechanism by a Strategic Ligand Modification on a Ruthenium Polypyridyl Catalyst
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Ben A. Johnson Dr. Somnath Maji Dr. Hemlata Agarwala Dr. Travis A. White Dr. Edgar Mijangos Prof. Dr. Sascha Ott 《Angewandte Chemie (International ed. in English)》2016,55(5):1825-1829
The introduction of a simple methyl substituent on the bipyridine ligand of [Ru(tBu3tpy)(bpy)(NCCH3)]2+ (tBu3tpy=4,4′,4′′‐tri‐tert‐butyl‐2,2′:6′,2′′‐terpyridine; bpy=2,2′‐bipyridine) gives rise to a highly active electrocatalyst for the reduction of CO2 to CO. The methyl group enables CO2 binding already at the one‐electron reduced state of the complex to enter a previously not accessible catalytic cycle that operates at the potential of the first reduction. The complex turns over with a Faradaic efficiency close to unity and at an overpotential that is amongst the lowest ever reported for homogenous CO2 reduction catalysts. 相似文献
14.
Kanidtha Hansongnern Uraiwan Saeteaw Jack Cheng Fen‐Ling Liao Tian‐Huey Lu 《Acta Crystallographica. Section C, Structural Chemistry》2001,57(8):895-896
The Ru—N bond distances in the title complex, [Ru(NO2)(C11H9N3)(C15H11N3)]BF4 or [Ru(NO2)(tpy)(azpy)]BF4, [tpy is 2,2′:6′,2′′‐terpyridine and azpy is 2‐(phenylazo)pyridine], are Ru—Npy 2.063 (4), Ru—Nazo 2.036 (4), Ru—Nnitro 2.066 (3) Å, and Ru—Ntpy 2.082 (4), 1.982 (3) and 2.074 (4) Å. The azo N atom is trans to the nitro group. The azo N=N bond length is 1.265 (5) Å, which is the shortest found in such complexes to date. This indicates a multiple bond between Ru and the N atom of the nitro group, and π‐backbonding [dπ(Ru) π*(azo)] is decreased. 相似文献
15.
Shunsuke Katagiri Dr. Ryota Sakamoto Hiroaki Maeda Dr. Yoshihiko Nishimori Tomochika Kurita Prof. Dr. Hiroshi Nishihara 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(16):5088-5096
This article completes our comprehensive understanding of the electron transport properties of our original π‐conjugated redox‐active molecular wires comprising Fe bridged by p‐phenylene linkers (tpy=2,2′:6′,2′′‐terpyridine). The Fe(tpy)2 oligomer wires comprise three types of tpy ligands: the anchor tpy ligand ( A series) makes a junction between the wire and electrode, the bridging bis‐tpy ligand ( L series) connects the Fe(tpy)2 units, and the terminal tpy ligand ( T series) possesses a redox site as a probe for the long‐range electron transport ability. Taking advantage of the precise tunability of the composition of the Fe(tpy)2 oligomer wires, thus far we investigated how A and L impacted on the electron‐transport ability. The excellent long‐range electron transport ability with ultrasmall attenuation constants (βd, 0.002 Å?1 as the minimum) depends on L significantly [Chem. Asian J. 2009 , 4, 1361], whereas A is unrelated to the βd value, but influences the zero‐distance electron‐transfer rate constant, ket0 [J. Am. Chem. Soc. 2010 , 132, 4524]. Herein we study the influence of terminal ligand T x (x=1–3). βd is independent of T , however, T3 , with a cyclometallated Ru complex as the redox site, gives rise to a ket0 value greater than T1 and T2 with ferrocene. This series of simple but definitive conclusions indicates that we have reached the stage of being able to precisely design molecular wires to attain desirable single‐molecule electron conduction. 相似文献
16.
Juan Granifo Beatriz Arvalo Rubn Gavio Sebastin Surez Ricardo Baggio 《Acta Crystallographica. Section C, Structural Chemistry》2016,72(12):932-938
4′‐Substituted derivatives of 2,2′:6′,2′′‐terpyridine with N‐containing heteroaromatic substituents, such as pyridyl groups, might be able to coordinate metal centres through the extra N‐donor atom, in addition to the chelating terpyridine N atoms. The incorporation of these peripheral N‐donor sites would also allow for the diversification of the types of noncovalent interactions present, such as hydrogen bonding and π–π stacking. The title compound, C24H16N4, consists of a 2,2′:6′,2′′‐terpyridine nucleus (tpy), with a pendant isoquinoline group (isq) bound at the central pyridine (py) ring. The tpy nucleus deviates slightly from planarity, with interplanar angles between the lateral and central py rings in the range 2.24 (7)–7.90 (7)°, while the isq group is rotated significantly [by 46.57 (6)°] out of this planar scheme, associated with a short Htpy…Hisq contact of 2.32 Å. There are no strong noncovalent interactions in the structure, the main ones being of the π–π and C—H…π types, giving rise to columnar arrays along [001], further linked by C—H…N hydrogen bonds into a three‐dimensional supramolecular structure. An Atoms In Molecules (AIM) analysis of the noncovalent interactions provided illuminating results, and while confirming the bonding character for all those interactions unquestionable from a geometrical point of view, it also provided answers for some cases where geometric parameters are not informative, in particular, the short Htpy…Hisq contact of 2.32 Å to which AIM ascribed an attractive character. 相似文献
17.
José Vicente Prof. Dr. José‐Antonio Abad Dr. María‐José López‐Sáez Dr. Peter G. Jones Prof. Dr. Delia Bautista Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(2):661-676
Complexes [Pd(C6H3XH‐2‐R′‐5)Y(N^N)] (X=O, NH; Y=Br, I; R′=H, NO2; N^N=N,N,N′,N′‐tetramethylethylenediamine (tmeda), 2,2′‐bipyridine (bpy), 4,4′‐di‐tert‐butyl‐2,2′‐bipyridine (dtbbpy)) react with RN?C?E (E=NR, S) or RC≡N (R=alkyl, aryl, NR′′2) and TlOTf (OTf=CF3SO3) to give, respectively, 1) products of the insertion of the C?E group into the C? Pd bond, protonation of the N atom, and coordination of X to Pd, [Pd{κ2‐X,E‐(XC6H3{EC(NHR)}‐2‐R′‐4)}(N^N)]OTf or [Pd(κ2‐X,N‐{ZC6H3(NH?CR)‐2‐R′‐4})(N^N)]OTf, or products of the coordination of carbodiimides and OH addition, [Pd{κ2‐C,N‐(C6H4{OC(NR)}NHR‐2)}(bpy)]OTf; or 2) products of the insertion of the C≡N group to Pd and N‐protonation, [Pd(κ2‐X,N‐{XC6H3(NH?CR)‐2‐R′‐4})(N^N)]OTf. 相似文献
18.
Triamidoamine–Uranium(IV)‐Stabilized Terminal Parent Phosphide and Phosphinidene Complexes
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Dr. Benedict M. Gardner Dr. Gábor Balázs Prof. Dr. Manfred Scheer Dr. Floriana Tuna Prof. Eric J. L. McInnes Dr. Jonathan McMaster Dr. William Lewis Prof. Alexander J. Blake Prof. Stephen T. Liddle 《Angewandte Chemie (International ed. in English)》2014,53(17):4484-4488
Reaction of [U(TrenTIPS)(THF)][BPh4] ( 1 ; TrenTIPS=N{CH2CH2NSi(iPr)3}3) with NaPH2 afforded the novel f‐block terminal parent phosphide complex [U(TrenTIPS)(PH2)] ( 2 ; U–P=2.883(2) Å). Treatment of 2 with one equivalent of KCH2C6H5 and two equivalents of benzo‐15‐crown‐5 ether (B15C5) afforded the unprecedented metal‐stabilized terminal parent phosphinidene complex [U(TrenTIPS)(PH)][K(B15C5)2] ( 4 ; U?P=2.613(2) Å). DFT calculations reveal a polarized‐covalent U?P bond with a Mayer bond order of 1.92. 相似文献
19.
A terpyridine derivative DPTP [di-(4-methylphenyl)-2,2':6',2"-terpyridine] was conveniently synthesized from 2-bromopyridine via halogen-dance reaction, Kharash coupling and Stille coupling reaction. Then its corresponding ruthenium complex Ru-DPTP [N,N,N-4,4''-di-(4-methy,phenyl)-2,2':6',2"-terpyridine-N,N,N-tris(is,-thi,cyanat,)- ruthenium(H) ammonium] was obtained and fully characterized by IR, UV-Vis, ESI MS and elemental analysis. The MLCT absorption band of Ru-DPTP was blue-shifted from 570 to 500 nm upon addition of Hg^2+. Among a series of surveyed metal ions, the complex showed a unique recognition to Hg^2+, indicating that it can be used as a selective colorimetric sensor for Hg^2+. 相似文献
20.
Igor V. Kazakov Michael Bodensteiner Alexey Y. Timoshkin 《Acta Crystallographica. Section C, Structural Chemistry》2014,70(3):312-314
The molecular structures of trichlorido(2,2′:6′,2′′‐terpyridine‐κ3N,N′,N′′)gallium(III), [GaCl3(C15H11N3)], and tribromido(2,2′:6′,2′′‐terpyridine‐κ3N,N′,N′′)gallium(III), [GaBr3(C15H11N3)], are isostructural, with the GaIII atom displaying an octahedral geometry. It is shown that the Ga—N distances in the two complexes are the same within experimental error, in contrast to expected bond lengthening in the bromide complex due to the lower Lewis acidity of GaBr3. Thus, masking of the Lewis acidity trends in the solid state is observed not only for complexes of group 13 metal halides with monodentate ligands but for complexes with the polydentate 2,2′:6′,2′′‐terpyridine donor as well. 相似文献