Graphene-like 2D coordination polymers (GCPs) have been of central research interest in recent decades with significant impact in many fields. According to classical coordination chemistry, Cu(II) can adopt the dsp2 hybridization to form square planar coordination geometry, but not Cu(I); this is why so far, there has been few 2D layered structures synthesized from Cu(I) precursors. Herein a pair of isostructural GCPs synthesized by the coordination of benzenehexathiol (BHT) ligands with Cu(I) and Cu(II) ions, respectively, is reported. Spectroscopic characterizations indicate that Cu(I) and Cu(II) coexist with a near 1:1 ratio in both GCPs but remain indistinguishable with a fractional oxidation state of +1.5 on average, making these two GCPs a unique pair of Creutz-Taube mixed-valence 2D structures. Based on density functional theory calculations, an intramolecular pseudo-redox mechanism is further uncovered whereby the radicals on BHT ligands can oxidize Cu(I) or reduce Cu(II) ions upon coordination, thus producing isostructures with distinct electron configurations. For the first time, it is demonstrated that using Cu(I) or Cu(II), one can achieve 2D isostructures, indicating an unusual fact that a neutral periodic structure can host a different number of total electrons as ground states, which may open a new chapter for 2D materials.
α-Hydroxy acids are prebiotic monomers that undergo dehydration synthesis to form polyester gels, which assemble into membraneless microdroplets upon aqueous rehydration. These microdroplets are proposed as protocells that can segregate and compartmentalize primitive molecules/reactions. Different primitive aqueous environments with a variety of salts could have hosted chemistries that formed polyester microdroplets. These salts could be essential cofactors of compartmentalized prebiotic reactions or even directly affect protocell structure. However, fully understanding polyester-salt interactions remains elusive, partially due to technical challenges of quantitative measurements in condensed phases. Here, spectroscopic and biophysical methods are applied to analyze salt uptake by polyester microdroplets. Inductively coupled plasma mass spectrometry is applied to measure the cation concentration within polyester microdroplets after addition of chloride salts. Combined with methods to determine the effects of salt uptake on droplet turbidity, size, surface potential and internal water distribution, it was observed that polyester microdroplets can selectively partition salt cations, leading to differential microdroplet coalescence due to ionic screening effects reducing electrostatic repulsion forces between microdroplets. Through applying existing techniques to novel analyses related to primitive compartment chemistry and biophysics, this study suggests that even minor differences in analyte uptake can lead to significant protocellular structural change.
Perovskite solar cells (PSC) have developed rapidly since the past decade with the aim to produce highly efficient photovoltaic technology at a low cost. Recently, physical and chemical defects at the buried interface of PSC including vacancies, impurities, lattice strain, and voids are identified as the next formidable hurdle to the further advancement of the performance of devices. The presence of these defects has unfavorably impacted many optoelectronic properties in the PSC, such as band alignment, charge extraction/recombination dynamics, ion migration behavior, and hydrophobicity. Herein, a broad but critical discussion on various essential aspects related to defects at the buried interface is provided. In particular, the defects existing at the surface of the underlying charge transporting layer (CTL) and the bottom surface of the perovskite film are initially elaborated. In situ and ex situ characterization approaches adopted to unveil hidden defects are elucidated to determine their influence on the efficiency, operational stability, and photocurrent-voltage hysteresis of PSC. A myriad of innovative strategies including defect management in CTL, the introduction of passivation materials, strain engineering, and morphological control used to address defects are also systematically elucidated to catalyze the further development of more efficient, reliable, and commercially viable photovoltaic devices.