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Understanding the landscape of molecular photocatalysis is vital to enable efficient conversion of feedstock molecules to targeted products and inhibit off-cycle reactivity. In this study, the light-promoted reactivity of [RuCp*2]+ was explored via electronic structure, photophysical, and photostability studies and the reactivity of [RuCp*2]+ within a photocatalytic hydrogen evolution cycle was assessed. TD-DFT calculations support the assignment of a low-energy ligand-to-metal charge transfer transition (LMCT) centered at 500 nm, where an electron from a ligand-based orbital delocalized across both Cp* ligands is promoted to a dx2–y2-based β-LUMO orbital. Upon irradiating the LMCT absorption feature, ultrafast transient absorption spectroscopy measurements show that an initial excited state (τ1 = 1.3 ± 0.1 ps) is populated, which undergoes fast relaxation to a longer-lived state (τ2 = 12.0 ± 0.9 ps), either via internal conversion or vibrational relaxation. Despite the short-lived nature of these excited states, bulk photolysis of [RuCp*2]+ demonstrates that photochemical conversion to decomposition products is possible upon prolonged illumination. Collectively, these studies reveal that [RuCp*2]+ undergoes light-driven decomposition, highlighting the necessity to construct molecular photocatalytic systems resistant to off-cycle reactivity in both the ground and excited states. 

Abstract Over the past decade, lead halide perovskite (LHP) nanocrystals (NCs) have attracted significant attention due to their tunable optoelectronic properties for next‐generation printed photonic and electronic devices. High‐energy photons in the presence of haloalkanes provide a scalable and sustainable pathway for precise bandgap engineering of LHP NCs via photo‐induced anion exchange reaction (PIAER) facilitated by in situ generated halide anions. However, the mechanisms driving photo‐induced bandgap engineering in LHP NCs remain not fully understood. This study elucidates the underlying PIAER mechanisms of LHP NCs through an advanced microfluidic platform. Additionally, the first instance of a PIAER, transforming CsPbBr₃NCs into high‐performing CsPbI₃NCs, with the assistance of a thiol‐based additive is reported. Utilizing an intensified photo‐flow microreactor accelerates the anion exchange rate 3.5‐fold, reducing material consumption 100‐fold compared to conventional batch processes. It is demonstrated that CsPbBr₃NCs act as photocatalysts, driving oxidative bond cleavage in dichloromethane and promoting the photodissociation of 1‐iodopropane using high‐energy photons. Furthermore, it is demonstrated that a thiol‐based additive plays a dual role: surface passivation, which enhances the photoluminescence quantum yield, and facilitates the PIAER. These findings pave the way for the tailored design of perovskite‐based optoelectronic materials. 

Although vibronic coupling phenomena have been recognized in the excited state dynamics of transition metal complexes, their impact on photoinduced electron transfer (PET) remains largely unexplored. This study investigates coherent wavepacket (CWP) dynamics during PET processes in a covalently linked electron donor–acceptor complex featuring a cyclometalated Pt(II) dimer as the donor and naphthalene diimide (NDI) as the acceptors. Upon photoexciting the Pt(II) dimer electron donor, ultrafast broadband transient absorption spectroscopy revealed direct modulation of NDI radical anion formation through certain CWP motions and correlated temporal evolutions of the amplitudes for these CWPs with the NDI radical anion formation. These results provide clear evidence that the CWP motions are the vibronic coherences coupled to the PET reaction coordinates. Normal mode analysis identified that the CWP motions originate from vibrational modes associated with the dihedral angles and bond lengths between the planes of the cyclometalating ligand and the NDI, the key modes altering their p-interaction, consequently influencing PET dynamics. The findings highlight the pivotal role of vibrations in shaping the favorable trajectories for the efficient PET processes. 

Abstract Color morphing refers to color change in response to an environmental stimulus. Photochromic materials allow color morphing in response to light, but almost all photochromic materials suffer from degradation when exposed to moist/humid environments or harsh chemical environments. One way of overcoming this challenge is by imparting chemical shielding to the color morphing materials via superomniphobicity. However, simultaneously imparting color morphing and superomniphobicity, both surface properties, requires a rational design. In this work, we systematically design color morphing surfaces with superomniphobicity through an appropriate combination of a photochromic dye, a low surface energy material, and a polymer in a suitable solvent (for one-pot synthesis), applied through spray coating (for the desired texture). We also investigate the influence of polymer polarity and material composition on color morphing kinetics and superomniphobicity. Our color morphing surfaces with effective chemical shielding can be designed with a wide variety of photochromic and thermochromic pigments and applied on a wide variety of substrates. We envision that such surfaces will have a wide range of applications including camouflage soldier fabrics/apparel for chem-bio warfare, color morphing soft robots, rewritable color patterns, optical data storage, and ophthalmic sun screening. 

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. 

Abstract Closed-loop, autonomous experimentation enables accelerated and material-efficient exploration of large reaction spaces without the need for user intervention. However, autonomous exploration of advanced materials with complex, multi-step processes and data sparse environments remains a challenge. In this work, we present AlphaFlow, a self-driven fluidic lab capable of autonomous discovery of complex multi-step chemistries. AlphaFlow uses reinforcement learning integrated with a modular microdroplet reactor capable of performing reaction steps with variable sequence, phase separation, washing, and continuous in-situ spectral monitoring. To demonstrate the power of reinforcement learning toward high dimensionality multi-step chemistries, we use AlphaFlow to discover and optimize synthetic routes for shell-growth of core-shell semiconductor nanoparticles, inspired by colloidal atomic layer deposition (cALD). Without prior knowledge of conventional cALD parameters, AlphaFlow successfully identified and optimized a novel multi-step reaction route, with up to 40 parameters, that outperformed conventional sequences. Through this work, we demonstrate the capabilities of closed-loop, reinforcement learning-guided systems in exploring and solving challenges in multi-step nanoparticle syntheses, while relying solely on in-house generated data from a miniaturized microfluidic platform. Further application of AlphaFlow in multi-step chemistries beyond cALD can lead to accelerated fundamental knowledge generation as well as synthetic route discoveries and optimization.