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Short-wave infrared (SWIR) light, 0.9–2.5 μm wavelengths, has widespread applications, including inspection processes, nighttime imaging, and machine vision. As such, there is increasing demand for practical and effective SWIR detectors. Many current SWIR photodetectors are based on high-cost materials and require cryogenic cooling. Perovskite materials, including CsPbI3, have been effectively used as photodetectors in the UV to near IR ranges, but their large bandgaps limit their use for lower energy SWIR light. In this report we introduce an all-inorganic perovskite photodetector based on CsPbI3 with heterojunction engineering for efficient and practical detection in the SWIR range at room temperature. The devices undergo a simple, solution-based fabrication process which includes spin-coating under ambient conditions and moderate annealing temperatures. Without additional cooling, the SWIR devices produce excellent results at room temperature with responsivity of 1.65 × 103 A W−1 and a specific detectivity of 8.0 × 1010 Jones under 0.28 mW cm−2 of 1310 nm light and bias of −5 V. This material shows not only high response but also high sensitivity, making it stand out in the field of SWIR photodetection with the additional benefits of low-cost production and room temperature operation. 

Bulk 2D electronic–vibrational (2D-EV) and 2D vibrational–electronic spectroscopies (2D-VE) were previously developed to correlate the electronic and vibrational degrees of freedom simultaneously, which allow for the study of couplings between electronic and vibrational transitions in photo-chemical systems. Such bulk-dominated methods have been used to extensively study molecular systems, providing unique information such as coherence sensitivity, molecular configurations, enhanced resolution, and correlated states and their dynamics. However, the analogy of interfacial 2D spectroscopy has fallen behind. Our recent work presented interface-specific 2D-EV spectroscopy (i2D-EV). In this work, we develop interface-specific two-dimensional vibrational–electronic spectroscopy (i2D-VE). The fourth-order spectroscopy is based on a Mach–Zehnder IR interferometer that accurately controls the time delay of an IR pump pulse pair for vibrational transitions, followed by broadband interface second-harmonic generation to probe electronic transitions. We demonstrate step-by-step how a fourth-order i2D-VE spectrum of AP3 molecules at the air/water interface was collected and analyzed. The line shape and signatures of i2D-VE peaks reveal solvent correlations and the spectral nature of vibronic couplings. Together, i2D-VE and i2D-EV spectroscopy provide coupling of different behaviors of the vibrational ground state or excited states with electronic states of molecules at interfaces and surfaces. The methodology presented here could also probe dynamic couplings of electronic and vibrational motions at interfaces and surfaces, extending the usefulness of the rich data that are obtained. 

Copper-catalyzed radical C(sp³)‒N coupling has become a major focus in synthetic catalysis over the past decade. However, achieving this reaction manifold by using enzymes has remained elusive. In this study, we introduce a photobiocatalytic approach for radical benzylic C(sp³)‒N coupling using a copper-substituted nonheme enzyme. Using rhodamine B as a photoredox catalyst, we identified a copper-substituted phenylalanine hydroxylase that facilitates enantioconvergent decarboxylative amination betweenN-hydroxyphthalimide esters and anilines. Directed evolution remodeled the active site, resulting in high enantioselectivities for most substrates. On the basis of molecular modeling and mechanistic studies, we propose that the enzyme accommodates a copper-anilide complex that reacts with a benzylic radical. This study expands the scope of non-natural biocatalytic transition metal catalysis to copper-catalyzed radical coupling. 

The movements of molecules at interfaces and surfaces are restricted by their asymmetric environments, leading to anisotropic orientational motions. In this work, in-plane orientational motions of the –C=O and –CF3 groups of coumarin 153 (C153) at the air/water interface were measured using time-resolved (TR) vibrational sum frequency generation (SFG). The in-plane orientational time constants of the –C=O and –CF3 groups of C153 are found to be 41.5 ± 8.2 and 36.0 ± 4.5 ps. These values are over five-times faster than that of 198 ± 15 ps for the permanent dipole of the whole C153 molecule at the interface, which may indicate that the two groups experience different interfacial friction in the plane. These differences could also be the result of the permanent dipole of C153 being almost five times those of the –C=O and –CF3 groups. The difference in orientational motions reveals the microscopic heterogeneous environment that molecules experience at the interface. While the interfacial dynamics of the two functional groups are similar, our TR-SFG experiments allowed the quantification of the in-plane dynamics of individual functional groups for the first time. Our experimental findings about the interfacial molecular motion have implications for molecular rotations, energy transfer, and charge transfer at material interfaces, photocatalysis interfaces, and biological cell/membrane aqueous interfaces.