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首页> 外文期刊>Chemistry: A European journal >The ~3[ndσ~*(n+1)pσ] Emissions of Linear Silver(I) and Gold(I) Chains withBridging Phosphine Ligands
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The ~3[ndσ~*(n+1)pσ] Emissions of Linear Silver(I) and Gold(I) Chains withBridging Phosphine Ligands

机译：桥联膦配体的线性银（I）和金（I）链的〜3 [ndσ〜*（n + 1）pσ]发射

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摘要

The complexes [Au_3(dcmp)_2][X]_3{dcmp =bis(dicyclohexylphosphi-nomethyl)cyclohexylphosphine; X=Cl (1), ClO)_4~- (2), OTf~- (3), PF_6~-(4),SCN~-(5)}, [Ag_3(dcmp)_2][ClO_4]_6), and[Ag_3(dcmp)_2Cl_2][ClO_4](7) were pre-pared and their structures were deter-mined by X-ray crystallography. Com-plexes 2-4 display a high-energy emis-sion band with λ_(max)at 442-452 nm,whereas 1 and 5 display a low-energyemission with λ_(max)at 558-634 nm inboth solid state and in dichlorome-thane at 298 K. The former is assignedto the ~3[5dσ~*6pσ] excited state of [Au_3-(dcmp)_2]~(3+), whereas the latter is attrib-uted to an exciplex formed betweenthe ~3[5dσ~*6pσ] excited state of [Au_3-(dcmp)_2[~(3+)and the counterions. Insolid state, complex [Ag_3(dcmp)_2]-[ClO_4]_3 (6) displays an intense emissionband at 375 nm with a Stokes shift of 7200 cm~(-1) from the ~1[4dσ~*?ú5pσ] ab-sorption band at 295 nm. The 375 nmemission band is assigned to the emis-sion directly from the ~3[4dσ~*5pσ] excit-ed state of 6. Density functional theory(DFT) calculations revealed that theabsorption and emission energies areinversely proportional to the numberof metal ions (n) in polynuclear Auand Ag~I linear chain complexes withoutclose metal???anion contacts. The emis-sion energies are extrapolated to be715 and 446 nm for the infinite linearAu~I and Ag~I chains, respectively, atmetal???metal distances of about 2.93-3.02 A. A QM/MM calculation on themodel [Au_3(dcmp)_2Cl_2]~+system, withAu???Cl contacts of 2.90-3.10 A, gaveoptimized Au???Au distances of 2.99-3.11 A in its lowest triplet excited stateand the emission energies were calcu-lated to be at approximately 600-690 nm, which are assigned to a three-coordinate Au~I site with its spectro-scopic properties affected by Au~I???Au~Iinteractions.
机译：配合物[Au_3（dcmp）_2] [X] _3 {dcmp =双（二环己基膦基-无甲基）环己基膦; X = Cl（1），ClO）_4〜-（2），OTf〜-（3），PF_6〜-（4），SCN〜-（5）}，[Ag_3（dcmp）_2] [ClO_4] _6）制备了[Ag_3（dcmp）_2Cl_2] [ClO_4]（7），并通过X射线晶体学测定了它们的结构。复合物2-4在442-452 nm处具有λ_（max）的高能发射带，而1和5在固态和固态下均在558-634 nm处具有λ_（max）的低能发射。二氯甲烷在298 K时。前者归属于[Au_3-（dcmp）_2]〜（3+）的〜3 [5dσ〜*6pσ]激发态，而后者归属于〜之间形成的激基复合物。 [Au_3-（dcmp）_2 [〜（3+）]和抗衡离子的3 [5dσ〜*6pσ]激发态。在固态下，复杂的[Ag_3（dcmp）_2]-[ClO_4] _3（6）在375 nm处显示出很强的发射带，从〜1 [4dσ〜*？ú5pσ] ab处的斯托克斯位移为7200 cm〜（-1）。在295nm处的吸收带。从〜3 [4dσ〜*5pσ]激发态直接将375 nm发射带分配给发射。密度泛函理论（DFT）计算表明，吸收和发射能与金属离子的数量成反比（ n）在没有紧密的金属阴离子接触的多核Auand Ag-1线性链络合物中。对于无限大的线性Au〜I和Ag〜I链，在金属???金属距离约为2.93-3.02 A时，发射能分别推断为715 nm和446 nm。在模型[Au_3（dcmp ）_2Cl_2]〜+系统，其Au的Cl接触为2.90-3.10 A，在其最低三重激发态下，Au的最佳Au距离为2.99-3.11 A，计算出的发射能约为600- 690nm，它被分配到一个三坐标的Au-I位点，其光谱特性受Au-I-Au-Iu-相互作用的影响。

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