Outer-sphere effects on ligand-field excited-state dynamics: solvent dependence of high-spin to low-spin conversion in [Fe(bpy)3]2+

In condensed phase chemistry, the solvent can have a significant impact on everything from yield to product distribution to mechanism. With regard to photo-induced processes, solvent effects have been well-documented for charge-transfer states wherein the redistribution of charge subsequent to light absorption couples intramolecular dynamics to the local environment of the chromophore. Ligand-field excited states are expected to be largely insensitive to such perturbations given that their electronic rearrangements are localized on the metal center and are therefore insulated from so-called outer-sphere effects by the ligands themselves. In contrast to this expectation, we document herein a nearly two-fold variation in the time constant associated with the ⁵T₂ → ¹A₁ high-spin to low-spin relaxation process of tris(2,2′-bipyridine)iron(ii) ([Fe(bpy)₃]²⁺) across a range of different solvents. Likely origins for this solvent dependence, including relevant solvent properties, ion pairing, and changes in solvation energy, were considered and assessed by studying [Fe(bpy)₃]²⁺ and related derivatives via ultrafast time-resolved absorption spectroscopy and computational analyses. It was concluded that the effect is most likely associated with the volume change of the chromophore arising from the interconfigurational nature of the ⁵T₂ → ¹A₁ relaxation process, resulting in changes to the solvent–solvent and/or solvent–solute interactions of the primary solvation shell sufficient to alter the overall reorganization energy of the system and influencing the kinetics of ground-state recovery.

Time-resolved spectroscopic measurements of ground-state recovery for [Fe(bpy)₃]²⁺ reveal that the solvent can induce an outer-sphere reorganization energy effect on excited-state dynamics involving metal-centered ligand-field electronic states.     

Synthesis of a Tweezer—like Bis（Phenylthiapropoxy）calix[4]—arene as a Cation／π Enhanced Sensor for Ion—Selective Electrodes

Two novel 25,27-dihydroxy-26,28-bis(3-phenylthiapropxy)-calix[4]arene(3) and 25,27-dihydroxy-26,28-bis(3-phenylthiapropoxy)-5,11,17,23-tetra-tert-butylcalix[4] arene (4) were synthesized for the evaluation of their ion-selectivity in ion-selective electrodes(ISEs).ISEs based on 3 and 4 as neutral ionophores were prepared,and their selectivity coefficients for Ag^ (lg KAg,M^pot)were investigated against other alkali metal,alkaline-earth metal,aluminum,thallium(Ⅰ）,Lead and some transition metal ions using the separate solution method (SSM).These ISEs showed excellent Ag^ seletivity over most of the interfering cations examined,except for Hg^2 and Fe^2 having relative smaller interference(lg KAg,M^pot≤-2.1).     

Zeolites with Continuously Tuneable Porosity

Zeolites are important materials whose utility in industry depends on the nature of their porous structure. Control over microporosity is therefore a vitally important target. Unfortunately, traditional methods for controlling porosity, in particular the use of organic structure‐directing agents, are relatively coarse and provide almost no opportunity to tune the porosity as required. Here we show how zeolites with a continuously tuneable surface area and micropore volume over a wide range can be prepared. This means that a particular surface area or micropore volume can be precisely tuned. The range of porosity we can target covers the whole range of useful zeolite porosity: from small pores consisting of 8‐rings all the way to extra‐large pores consisting of 14‐rings.     

Synthesis of mono-substituted 2,2'-bipyridines

The rapid synthesis of 4-aryl-2,2'-bipyridines is described leading to some previously reported compounds in good yields in addition to some new functionalized bipyridines.     

高能强子–强子碰撞中喷注性质的蒙特卡洛研究

在喷注“圆锥判定法”的基础上,对高能强子–强子碰撞中产生的喷注(微喷注)的性质进行了蒙特卡洛研究.采用以喷注动量为z轴的“喷注坐标系”,给出了表征喷注性质的各物理量在新坐标系中的分布情况.结果表明,圆锥判定法能够作为一种有效手段来对高能强子–强子碰撞和相对论重离子碰撞中发生的硬和半硬过程开展实验研究.由有喷注事件和无喷注事件的多重数分布可以看到,E_t=2GeV是用圆锥法确定喷注的合理的横能截断值.     

Laser-hole boring into overdense plasmas measured with soft X-Ray laser probing

A laser self-focused channel formation into overdense plasmas was observed using a soft x-ray laser probe system with a grid image refractometry (GIR) technique. 1.053 &mgr;m laser light with a 100 ps pulse duration was focused onto a preformed plasma at an intensity of 2x10(17) W/cm (2). Cross sections of the channel were obtained which show a 30 &mgr;m diameter in overdense plasmas. The channel width in the overdense region was kept narrow as a result of self-focusing. Conically diverging density ridges were also observed along the channel, indicating a Mach cone created by a shock wave due to the supersonic propagation of the channel front.     

Synthesis and spectroscopic characterization of CN-substituted bipyridyl complexes of Ru(II)

A series of ruthenium complexes having the general form [Ru(bpy)(3-n)(CN-Me-bpy)(n)](PF(6))(2) (where bpy = 2,2'-bipyridine, CN-Me-bpy = 4,4'-dicyano-5,5'-dimethyl-2,2'-bipyridine, and n = 1-3 for complexes 1-3, respectively) have been synthesized and characterized using a variety of steady-state and nanosecond time-resolved spectroscopies. Electrochemical measurements indicate that the CN-Me-bpy ligand is significantly easier to reduce than the unsubstituted bipyridine (on the order of ～500 mV), implying that the lowest energy (3)MLCT (metal-to-ligand charge transfer) state will be associated with the CN-Me-bpy ligand(s) in all three compounds. Comparison of the Huang-Rhys factors derived from spectral fitting analyses of the steady state emission spectra of complexes 1-3 suggests all three compounds are characterized by excited-state geometries that are less distorted relative to their ground states as compared to [Ru(bpy)(3)](PF(6))(2); the effect of the more nested ground- and excited-state potentials is reflected in the unusually high radiative quantum yields (13% (1), 27% (2), and 40% (3)) and long (3)MLCT-state room-temperature lifetimes (1.6 μs, 2.6 μs, and 3.5 μs, respectively) for these compounds. Coupling of the π* system into the CN groups is confirmed by nanosecond step-scan IR spectra which reveal a ～40 cm(-1) bathochromic shift of the CN stretching frequency, indicative of a weaker CN bond in the (3)MLCT excited state relative to the ground state. The fact that the shift is the same for complexes 1-3 is evidence that, in all three complexes, the long-lived excited state is localized on a single CN-Me-bpy ligand rather than being delocalized over multiple ligands.     

Bidirectional "ping-pong" energy transfer and 3000-fold lifetime enhancement in a Re(I) charge transfer complex

The synthesis and photophysics of a new Re(I)-carbonyl diimine complex, Re(PNI-phen)(CO)(3)Cl, where the PNI-phen is N-(1,10-phenanthroline)-4-(1-piperidinyl)naphthalene-1,8-dicarboximide is reported. The metal-to-ligand charge transfer (MLCT) emission lifetime was increased approximately 3000-fold at room temperature with respect to that of the model complex [Re(phen)(CO)(3)Cl] as a result of thermal equilibrium between the emissive (3)MLCT state and a long-lived triplet ligand-centered ((3)LC) state on the PNI chromophore. This represents the longest excited state lifetime (τ = 651 μs) that has ever been observed for a Re(I)-based CT photoluminescence at room temperature. The energy transfer processes and the associated rate constants leading to the establishment of the excited state equilibrium were elucidated by a powerful combination of three techniques (transient visible and infrared (IR) absorption and photoluminescence), each applied from ultrafast to the micro/milliseconds time scale. The MLCT excited state was monitored by transient IR using CO vibrations through time intervals where the corresponding signals obtained in conventional visible transient absorption were completely obscured by overlap with strong transients originating from the pendant PNI chromophore. Following initial excitation of the (1)LC state on the PNI chromophore, energy is transferred to form the MLCT state with a time constant of 45 ps, a value confirmed in all three measurement domains within experimental error. Although transient spectroscopy confirms the production of the (3)MLCT state on ultrafast time scales, Fo?rster resonance energy transfer calculations using the spectral properties of the two chromophores support initial singlet transfer from (1)PNI* to produce the (1)MLCT state by the agreement with the experimentally observed energy transfer time constant and efficiency. Intersystem crossing from the (1)MLCT to the (3)MLCT excited state is believed to be extremely fast and was not resolved with the current experiments. Finally, triplet energy was transferred from the (3)MLCT to the PNI-centered (3)LC state in less than 15 ns, ultimately achieving equilibrium between the two excited states. Subsequent relaxation to the ground state occurred via emission resulting from thermal population of the (3)MLCT state with a resultant lifetime of 651 μs. The title chromophore represents an interesting example of "ping-pong" energy transfer wherein photon excitation first migrates away from the initially prepared (1)PNI* excited state and then ultimately returns to this moiety as a long-lived excited triplet which disposes of its energy by equilibrating with the photoluminescent Re(I) MLCT excited state.     

Composing dinatural transformations: Towards a calculus of substitution

Dinatural transformations, which generalise the ubiquitous natural transformations to the case where the domain and codomain functors are of mixed variance, fail to compose in general; this has been known since they were discovered by Dubuc and Street in 1970. Many ad hoc solutions to this remarkable shortcoming have been found, but a general theory of compositionality was missing until Petri?, in 2003, introduced the concept of g-dinatural transformations, that is, dinatural transformations together with an appropriate graph: he showed how acyclicity of the composite graph of two arbitrary dinatural transformations is a sufficient and essentially necessary condition for the composite transformation to be in turn dinatural. Here we propose an alternative, semantic rather than syntactic, proof of Petri?'s theorem, which the authors independently rediscovered with no knowledge of its prior existence; we then use it to define a generalised functor category, whose objects are functors of mixed variance in many variables, and whose morphisms are transformations that happen to be dinatural only in some of their variables.We also define a notion of horizontal composition for dinatural transformations, extending the well-known version for natural transformations, and prove it is associative and unitary. Horizontal composition embodies substitution of functors into transformations and vice-versa, and is intuitively reflected from the string-diagram point of view by substitution of graphs into graphs.This work represents the first, fundamental steps towards a substitution calculus for dinatural transformations as sought originally by Kelly, with the intention then to apply it to describe coherence problems abstractly. There are still fundamental difficulties that are yet to be overcome in order to achieve such a calculus, and these will be the subject of future work; however, our contribution places us well in track on the path traced by Kelly towards a calculus of substitution for dinatural transformations.