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Abstract Surface functionalization and colloidal stability are pivotal for numerous applications of gold nanoparticles (Au‐NPs). Over the past decade, N‐heterocyclic carbenes (NHCs) have emerged as promising ligands for stabilizing Au‐NPs owing to their ease of synthesis, structural diversity, and strong metal‐ligand bonds. Here, we introduce new Au(I)–NHCcopolymer scaffolds as precursors to multidentate NHC‐protected Au‐NPs. Ring‐opening metathesis copolymerization of a norbornene‐appended Au(I)−NHC complex with another functionalized norbornene comonomer provides NHC–Au(I) copolymers with modular compositions and structures. Upon reduction, these copolymers yield multidentate polyNHC‐coated Au‐NPs with varied properties and corona functionalities dictated by the secondary monomer. These nanoparticles exhibit excellent size homogeneity and stability against aggregation in various buffers, cell culture media, and under exposure to electrolytes, oxidants, and exogenous thiols over extended periods. Moreover, we demonstrate post‐synthetic surface functionalization reactions of polyNHC−Au‐NPs while maintaining colloidal stability, highlighting their robustness and potential for applications such as bioconjugation. Overall, these findings underscore the potential of ROMP‐derived NHC‐containing copolymers as highly tunable and versatile multidentate ligands that may be suitable for other inorganic colloids and flat surfaces. 

Nitrogen-vacancy (NV) centers in diamond are a promising platform for nanoscale NMR sensing. Despite significant progress toward using NV centers to detect and localize nuclear spins down to the single spin level, NV-based spectroscopy of individual, intact, arbitrary target molecules remains elusive. Such sensing requires that target molecules are immobilized within nanometers of NV centers with long spin coherence. The inert nature of diamond typically requires harsh functionalization techniques such as thermal annealing or plasma processing, limiting the scope of functional groups that can be attached to the surface. Solution-phase chemical methods can be readily generalized to install diverse functional groups, but they have not been widely explored for single-crystal diamond surfaces. Moreover, realizing shallow NV centers with long spin coherence times requires highly ordered single-crystal surfaces, and solution-phase functionalization has not yet been shown with such demanding conditions. In this work, we report a versatile strategy to directly functionalize C–H bonds on single-crystal diamond surfaces under ambient conditions using visible light, forming C–F, C–Cl, C–S, and C–N bonds at the surface. This method is compatible with NV centers within 10 nm of the surface with spin coherence times comparable to the state of the art. As a proof-of-principle demonstration, we use shallow ensembles of NV centers to detect nuclear spins from surface-bound functional groups. Our approach to surface functionalization opens the door to deploying NV centers as a tool for chemical sensing and single-molecule spectroscopy. 

Two new aromatic pyrimidine-based derivatives designed specifically for halogen bond directed self-assembly are investigated through a combination of high-resolution Raman spectroscopy, X-ray crystallography, and computational quantum chemistry. The vibrational frequencies of these new molecular building blocks, pyrimidine capped with furan (PrmF) and thiophene (PrmT), are compared to those previously assigned for pyrimidine (Prm). The modifications affect only a select few of the normal modes of Prm, most noticeably its signature ring breathing mode, ν1. Structural analyses afforded by X-ray crystallography, and computed interaction energies from density functional theory computations indicate that, although weak hydrogen bonding (C–H···O or C–H···N interactions) is present in these pyrimidine-based solid-state co-crystals, halogen bonding and π-stacking interactions play more dominant roles in driving their molecular-assembly. 

Iodine binding to thiophene rings in dyes for dye-sensitized solar cells (DSCs) has been hypothesized to be performance degrading in a number of literature cases. Binding of iodine to dyes near the semiconductor surface can promote undesirable electron transfers and lower the overall efficiency of devices. Six thiophene or furan containing dye analogs were synthesized to analyze iodine binding to the dyes via Raman spectroscopy, UV-Vis studies, device performance metrics and density functional theory (DFT) based computations. Evidence suggests I 2 binds thiophene-based dyes stronger than furan-based dyes. This leads to higher DSC device currents and voltages from furan analogues, and longer electron lifetimes in DSC devices using furan based dyes. Raman spectrum of the TiO 2 surface-bound dyes reveals additional and more instense peaks for thiophene dyes in the presence of I 2 relative to no I 2 . Additionally, broader and shifted UV-Vis peaks are observed for thiophene dyes in the presence of I 2 on TiO 2 films suggesting significant interaction between the dye molecules and I 2 . These observations are also supported by DFT and TD-DFT calculations which indicate the absence of a key geometric energy minimum in the dye–I 2 ground state for furan dyes which are readily observed for the thiophene based analogues.