skip to main content

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


  • NSF Public Access
  • Search Results
  • Temperature dependence of photophysical properties of a dinuclear C^N-cyclometalated Pt( ii ) complex with an intimate Pt–Pt contact. Zero-field splitting and sub-state decay rates of the lowest triplet
Title: Temperature dependence of photophysical properties of a dinuclear C^N-cyclometalated Pt( ii ) complex with an intimate Pt–Pt contact. Zero-field splitting and sub-state decay rates of the lowest triplet
The temperature dependence (1.7 K < T < 100 K) of emission decay is reported for the first time for a type of di-nuclear Pt complex featuring a metal–metal-to-ligand charge transfer (MMLCT) lowest energy transition that arises from a strong Pt–Pt interaction. The effect of local variation of the host/guest cage in a polymer matrix upon the phosphorescence decay time constants is characterized by the Kohlrausch–Williams–Watts function. The temperature dependence of the average decay time constants is fit by a Boltzmann-type expression to obtain the average zero-field splittings and individual sublevel decay rates of the photoluminescent triplet excited state.  more » « less
Award ID(s):
1665033
PAR ID:
10103955
Author(s) / Creator(s):
; ; ; ;
Date Published:
Journal Name:
Physical Chemistry Chemical Physics
Volume:
20
Issue:
38
ISSN:
1463-9076
Page Range / eLocation ID:
25096 to 25104
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; ; ; ; ; ; ; ( , Nanoscale)
    null (Ed.)
    A phase transition material, VO 2 , with a semiconductor-to-metal transition (SMT) near 341 K (68 °C) has attracted significant research interest because of drastic changes in its electrical resistivity and optical dielectric properties. To address its application needs at specific temperatures, tunable SMT temperatures are highly desired. In this work, effective transition temperature ( T c ) tuning of VO 2 has been demonstrated via a novel Pt : VO 2 nanocomposite design, i.e. , uniform Pt nanoparticles (NPs) embedded in the VO 2 matrix. Interestingly, a bidirectional tuning has been achieved, i.e. , the transition temperature can be systematically tuned to as low as 329.16 K or as high as 360.74 K, with the average diameter of Pt NPs increasing from 1.56 to 4.26 nm. Optical properties, including transmittance ( T %) and dielectric permittivity ( ε ′) were all effectively tuned accordingly. All Pt : VO 2 nanocomposite thin films maintain reasonable SMT properties, i.e. sharp phase transition and narrow width of thermal hysteresis. The bidirectional T c tuning is attributed to two factors: the reconstruction of the band structure at the Pt : VO 2 interface and the change of the Pt : VO 2 phase boundary density. This demonstration sheds light on phase transition tuning of VO 2 at both room temperature and high temperature, which provides a promising approach for VO 2 -based novel electronics and photonics operating under specific temperatures. 
    more » « less
  2. ; ; ; ; ( , Dalton Transactions)
    Dinuclear d 8 Pt( ii ) complexes, where two mononuclear square planar Pt( ii ) units are bridged in an “A-frame” geometry, possess photophysical properties characterised by either metal-to-ligand-(MLCT) or metal–metal–ligand-to-ligand charge transfer (MMLCT) transitions determined by the distance between the two Pt( ii ) centres. When using 8-hydroxyquinoline (8HQH) as the bridging ligand to construct novel dinuclear complexes with general formula [C^NPt(μ-8HQ)] 2 , where C^N is either 2-phenylpyridine (1) or 7,8-benzoquinoline (2), triplet ligand-centered ( 3 LC) photophysics results echoing that in a mononuclear model chromophore, [Pt(8HQ) 2 ] (3). The lengthened Pt–Pt distances of 3.255 Å (1) and 3.243 Å (2) results in a lowest energy absorption centred around 480 nm assigned as having mixed LC/MLCT character by TD-DFT, mirroring the visible absorption spectrum of 3. Additionally, 1 and 2 exhibit 3 LC photoluminescence with limited quantum yields (0.008) from broad transitions centred near 680 nm. Photoexcitation of 1–3 leads to an initially prepared excited state that relaxes within 15 ps to a 3 LC excited state centred on the 8HQ bridge, which then persists for several microseconds. All the experimental results correspond well with DFT electronic structure calculations. 
    more » « less
  3. ; ; ; ; ; ; ( , Faraday Discussions)
    Ultrafast excited state processes of transition metal complexes (TMCs) are governed by complicated interplays between electronic and nuclear dynamics, which demand a detailed understanding to achieve optimal functionalities of photoactive TMC-based materials for many applications. In this work, we investigated a cyclometalated platinum( ii ) dimer known to undergo a Pt–Pt bond contraction in the metal–metal-to-ligand-charge-transfer (MMLCT) excited state using femtosecond broadband transient absorption (fs-BBTA) spectroscopy in combination with geometry optimization and normal mode calculations. Using a sub-20 fs pump and broadband probe pulses in fs-BBTA spectroscopy, we were able to correlate the coherent vibrational wavepacket (CVWP) evolution with the stimulated emission (SE) dynamics of the 1 MMLCT state. The results demonstrated that the 145 cm −1 CVWP motions with the damping times of ∼0.9 ps and ∼2 ps originate from coherent Pt–Pt stretching vibrations in the singlet and triplet MMLCT states, respectively. On the basis of excited state potential energy surface calculations in our previous work, we rationalized that the CVWP transfer from the Franck–Condon (FC) state to the 3 MMLCT state was mediated by a triplet ligand-centered ( 3 LC) intermediate state through two step intersystem crossing (ISC) on a time scale shorter than a period of the Pt–Pt stretching wavepacket motions. Moreover, it was found that the CVWP motion had 110 cm −1 frequency decays with the damping time of ∼0.2 ps, matching the time constant of 0.253 ps, corresponding to a redshift in the SE feature at early times. This observation indicates that the Pt–Pt bond contraction changes the stretching frequency from 110 to 145 cm −1 and stabilizes the 1 MMLCT state relative to the 3 LC state with a ∼0.2 ps time scale. Thus, the ultrafast ISC from the 1 MMLCT to the 3 LC states occurs before the Pt–Pt bond shortening. The findings herein provide insight into understanding the impact of Pt–Pt bond contraction on the ultrafast branching of the 1 MMLCT population into the direct ( 1 MMLCT → 3 MMLCT) and indirect ISC pathways ( 1 MMLCT → 3 LC → 3 MMLCT) in the Pt( ii ) dimer. These results revealed intricate excited state electronic and nuclear motions that could steer the reaction pathways with a level of detail that has not been achieved before. 
    more » « less
  4. ; ; ; ; ; ; ( , The Journal of Chemical Physics)
    The effect of gases on the surface composition of Cu–Pt bimetallic catalysts has been tested by in situ infrared (IR) and x-ray absorption spectroscopies. Diffusion of Pt atoms within the Cu–Pt nanoparticles was observed both in vacuum and under gaseous atmospheres. Vacuum IR spectra of CO adsorbed on CuPt x /SBA-15 catalysts (x = 0–∞) at 125 K showed no bonding on Pt regardless of Pt content, but reversible Pt segregation to the surface was seen with the high-Pt-content (x ≥ 0.2) samples upon heating to 225 K. In situ IR spectra in CO atmospheres also highlighted the reversible segregation of Pt to the surface and its diffusion back into the bulk when cycling the temperature from 295 to 495 K and back, most evidently for diluted single-atom alloy catalysts (x ≤ 0.01). Similar behavior was possibly observed under H 2 using small amounts of CO as a probe molecule. In situ x-ray absorption near-edge structure data obtained for CuPt 0.2 /SBA-15 under both CO and He pointed to the metallic nature of the Pt atoms irrespective of gas or temperature, but analysis of the extended x-ray absorption fine structure identified a change in coordination environment around the Pt atoms, from a (Pt–Cu):(Pt–Pt) coordination number ratio of ∼6:6 at or below 445 K to 8:4 at 495 K. The main conclusion is that Cu–Pt bimetallic catalysts are dynamic, with the composition of their surfaces being dependent on temperature in gaseous environments. 
    more » « less
  5. ; ; ; ; ; ; ; ; ; ( , Advanced Materials)
    Abstract

    Acting like thermal resistances, ferroelectric domain walls can be manipulated to realize dynamic modulation of thermal conductivity (k), which is essential for developing novel phononic circuits. Despite the interest, little attention has been paid to achieving room‐temperature thermal modulation in bulk materials due to challenges in obtaining a high thermal conductivity switching ratio (khigh/klow), particularly in commercially viable materials. Here, room‐temperature thermal modulation in 2.5 mm‐thick Pb(Mg1/3Nb2/3)O3–xPbTiO3(PMN–xPT) single crystals is demonstrated. With the use of advanced poling conditions, assisted by the systematic study on composition and orientation dependence of PMN–xPT, a range of thermal conductivity switching ratios with a maximum of ≈1.27 is observed. Simultaneous measurements of piezoelectric coefficient (d33) to characterize the poling state, domain wall density using polarized light microscopy (PLM), and birefringence change using quantitative PLM reveal that compared to the unpoled state, the domain wall density at intermediate poling states (0<d33<d33,max) is lower due to the enlargement in domain size. At optimized poling conditions (d33,max), the domain sizes show increased inhomogeneity that leads to enhancement in the domain wall density. This work highlights the potential of commercially available PMN–xPT single crystals among other relaxor‐ferroelectrics for achieving temperature control in solid‐state devices.

     
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email