130269-70-4Relevant academic research and scientific papers
Broadband visible-light-harvesting trans-bis(alkylphosphine) platinum(II)-alkynyl complexes with singlet energy transfer between BODIPY and naphthalene diimide ligands
Liu, Lianlian,Guo, Song,Ma, Jie,Xu, Kejing,Zhao, Jianzhang,Zhang, Tierui
, p. 14282 - 14295 (2014)
A heteroleptic bis(tributylphosphine) platinum(II)-alkynyl complex (Pt-1) showing broadband visible-light absorption was prepared. Two different visible-light-absorbing ligands, that is, ethynylated boron-dipyrromethene (BODIPY) and a functionalized naphthalene diimide (NDI) were used in the molecule. Two reference complexes, Pt-2 and Pt-3, which contain only the NDI or BODIPY ligand, respectively, were also prepared. The coordinated BODIPY ligand shows absorption at 503 nm and fluorescence at 516 nm, whereas the coordinated NDI ligand absorbs at 594 nm; the spectral overlap between the two ligands ensures intramolecular resonance energy transfer in Pt-1, with BODIPY as the singlet energy donor and NDI as the energy acceptor. The complex shows strong absorption in the region 450 nm-640 nm, with molar absorption coefficient up to 88 000 m-1 cm-1. Longlived triplet excited states lifetimes were observed for Pt-1-Pt-3 (36.9 μs, 28.3 μs, and 818.6 μs, respectively). Singlet and triplet energy transfer processes were studied by the fluorescence/ phosphorescence excitation spectra, steady-state and time-resolved UV/Vis absorption and luminescence spectra, as well as nanosecond time-resolved transient difference absorption spectra. A triplet-state equilibrium was observed for Pt-1. The complexes were used as triplet photosensitizers for triplet-triplet annihilation upconversion, with upconversion quantum yields up to 18.4% being observed for Pt-1.
Near - IR Broadband-Absorbing trans -Bisphosphine Pt(II) Bisacetylide Complexes: Preparation and Study of the Photophysics
Yang, Wenbo,Karatay, Ahmet,Zhao, Jianzhang,Song, Jian,Zhao, Liang,Xing, Yongheng,Zhang, Caishun,He, Cheng,Yaglioglu, Halime Gul,Hayvali, Mustafa,Elmali, Ayhan,Küük?z, Betül
, p. 7492 - 7505 (2015)
Broadband near-IR absorbing trans-bis(trialkylphosphine) Pt(II) bisacetylide binuclear complex (Pt-1) was prepared with boron-dipyrromethene (Bodipy) and styrylBodipy acetylide ligands. Pt-1 shows strong absorption bands at 731 and 503 nm. Singlet energy transfer (EnT) and efficient intersystem crossing of the central coordinated Bodipy ligand were proposed to be responsible for the efficient funneling of the excitation energy to the triplet-state manifold. Reference complexes containing only a single Bodipy ligand were prepared for comparison (with styrylBodipy ligand Pt-0 or Bodipy ligand Pt-2). The molecular structures were confirmed by single-crystal X-ray diffraction. The photophysical properties were studied with steady-state and time-resolved transient absorption spectroscopies, electrochemical characterization, and density functional theory/time-dependent density functional theory calculations. Dual fluorescence was observed for Pt-1. Singlet EnT in Pt-1 was proposed based on the fluorescence quenching/excitation spectra, and femtosecond transient absorption spectra (energy transfer rate constant kEnT = 2.2 × 1010 s-1). With nanosecond transient absorption spectra, intramolecular triplet-state energy transfer in Pt-1 was proved. Gibbs free energy changes of charge separation indicate that the photoinduced intramolecular electron transfer in Pt-1 is thermodynamically prohibited. Intermolecular triplet transfer between Pt-2 and L-1 was studied with nanosecond transient absorption spectra; the EnT rate and energy transfer efficiency were determined as 3.6 × 104 s-1 and 94.5%, respectively. The singlet oxygen (1O2) photosensitizing of Pt-1 was improved as compared to the complexes containing only a single visible-light-absorbing chromophore.
Platinum(II) acetylide complexes with star- and V-shaped configurations possessing good trade-off between optical transparency and optical power limiting performance
Yao,Tian,Jin,Zhao,Sun,Yang,Zhou,Wong
, p. 11672 - 11682 (2017/11/30)
By employing the central ligand with the desired structures, two series of Pt(ii) acetylide complexes containing dimesitylborane (-B(Mes)2) and phenyl units as the terminal groups with star- and V-shaped configurations have been synthesized. Photophysical investigations have indicated that the -B(Mes)2 group can enhance triplet (T1) emission of the concerned Pt(ii) acetylide molecules by enhancing the mixing of molecular orbitals from organic ligands and Pt(ii) centers. The much higher T1 emission intensity associated with TEB-Pt-B, CAZ-Pt-B and TPA-Pt-B can render them much stronger optical power limiting (OPL) response than their counterparts, TEB-Pt-Ph, CAZ-Pt-Ph and TPA-Pt-Ph respectively, terminated with phenyl groups. In addition, OPL ability of TPA-Pt-B for 532 nm nanosecond laser pulse can even surpass that of state-of-the-art OPL material C60. In addition, most Pt(ii) acetylide complexes show OPL figure of merit factor σex/σo higher than that of C60. Importantly, the star-shaped molecular configuration employed by the Pt(ii) acetylide units has the advantage of introducing more Pt(ii) centers to the molecular skeleton while maintaining optical transparency of the concerned Pt(ii) acetylide complexes. So, this research can open a new outlet for fulfilling the optimized trade-off between OPL activity and optical transparency for OPL materials based on reverse saturable absorption (RSA) mechanism.
Visible light-harvesting trans bis(alkylphosphine) platinum(ii)-alkynyl complexes showing long-lived triplet excited states as triplet photosensitizers for triplet-triplet annihilation upconversion
Liu, Lianlian,Huang, Dandan,Draper, Sylvia M.,Yi, Xiuyu,Wu, Wanhua,Zhao, Jianzhang
, p. 10694 - 10706 (2013/09/12)
Symmetric and asymmetric linear trans-bis(tributylphosphine) Pt(ii) bis(acetylide) complexes with functionalized aryl alkynyl ligands (coumarin, naphthalimide and phenyl acetylides) were prepared, which show enhanced absorption in the visible region (mola
Spectroscopic characterization of a series of platinum acetylide complexes having a localized triplet exciton
Cooper, Thomas M.,Krein, Douglas M.,Burke, Aaron R.,McLean, Daniel G.,Rogers, Joy E.,Slagle, Jonathan E.,Fleitz, Paul A.
, p. 4369 - 4375 (2008/10/09)
In this work, we describe the spectroscopic properties of a series of platinum complexes containing one acetylide ligand per platinum, having the chemical formula trans-Pt(PBu3)2((C≡CC 6H4)n-H)Cl, n = 1-3 (designated as half-PEn-Pt) and compare their spectroscopic behavior with the well-characterized series trans-Pt(PBu3)2((C≡CC6H4) n-H)2, n = 1-3 (designated as PEn-Pt). This comparison aims to determine if the triplet state of PEn-Pt is confined to one ligand or delocalized across the central platinum atom. We measured ground-state absorption spectra, fluorescence spectra, phosphorescence spectra, and triplet-state absorption spectra. The ground-state absorption spectra and fluorescence spectra both showed a blue shift when comparing half-PEn-Pt with PEn-Pt, showing the Si state is delocalized across the platinum. In contrast, the phosphorescence spectra of the two types of compounds had the same 0-0 band energy, showing the T1 state was confined to one ligand in PEn-Pt. The triplet state absorption spectra blue shifted when comparing half-PEn-Pt with PEn-Pt, showing the Tn state was delocalized across the central platinum. This comparison supports recently published work that suggested this confinement effect
Preparation of models and oligomers of metal alkynyls NMR, GPC and X-ray structural characterization of building blocks for the construction of molecular devices
La Groia, Alessandra,Ricci, Antonella,Bassetti, Mauro,Masi, Dante,Bianchini, Claudio,Lo Sterzo, Claudio
, p. 406 - 420 (2007/10/03)
A systematic study has been carried out for the use of the palladium-based Extended One Pot (EOP) synthetic protocol toward the preparation of metal alkynyl oligomers of general formula [- C≡C-Ar-C≡C-M(L)m -]n (M=Pt, Pd). Model compounds of type trans-M(PBu 3)2(C≡CC6H5) 2 have been prepared by the reaction of tributyltinethynylbenzene with trans-M(PBu3)2 Cl2, in the absence of palladium catalysis, since the presence of catalytic Pd(PPh3)4 yields reaction mixtures containing starting material, product and intermediate complex trans-MCl (PBu3)2(C≡CC6H5). Palladium catalysis has been used for the formation of the bistinacetylide compounds Bu3Sn-C≡C- Ar-C≡C-SnBu3 (Ar=C6 H4; bis(2,5-n-octyloxy)C6H4). Subsequent coupling of these compounds with MCl2(PBu3) 2 in the absence of palladium catalyst yields metal alkynyl oligomers. Comparison of 31P-NMR and gel permeation chromatography (GPC) analyses indicates that the GPC technique represents a reliable method to estimate polymer chain lengths for polymers bearing branched aromatic spacers, in spite of the rigid-rod shape of the polymer backbone. Single crystal X-ray determinations of model compounds demonstrate the essential role of side substituents in the aromatic ring to control the supramolecular order and, as a consequence, the optoelectronic properties of materials.
