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Electrochromic devices have widespread application potential, but the currently available switching speeds limit broad real-world implementation of this technology. Here, we report surface-engineered two-dimensional polymers with ionophilic pores that offer unprecedented switching speeds in solid-state, two-terminal, electrochromic devices. In particular, we demonstrate that a crystalline donor–acceptor 2DP functionalized with ethylene glycol oligomers exhibits multistate infrared absorption that is 4× faster (t_c = 320 ms) with 3× coloration efficiency (491 cm² C^–1) compared to an alkyl functionalized 2DP constructed from the same chromophores. The functionalized nanoporous surfaces enable rapid switching in these materials under either oxidative or reductive conditions, allowing usmore » to access a range of robust, stable optical responses in a single electrochromic layer. These attributes led us to leverage surface-functionalized 2DPs as multistate infrared logic gates. Collectively, this work demonstrates that surface engineering of nanoporous crystalline lattices is a promising approach to co-optimize the electronic and ionic conductivities required to achieve rapidly switchable electrochromic layers. Beyond speed and efficiency, the demonstration of multistate infrared characteristics shows that electrochromic frameworks are useful in integrated optoelectronic circuits. This positions surface-engineered 2DPs as improved electrochromic coatings and a new material platform for photonic information processing and adaptive devices.« less

The ability to perform versatile covalent surface modifications in two-dimensional (2D) inorganic materials marks a significant advance in the functionalization of this broad family of materials. One particularly successful example of 2D materials with chemically modifiable surfaces are 2D transition metal carbides and nitrides (MXenes). MXenes' strong in-plane metal-carbon bonds and labile surface metal-halide bonds create altogether unprecedented opportunities for versatile postsynthetic modifications and assembling complex materials, including various organic-inorganic hybrids. Here, we demonstrate the general applicability of this surface modification strategy to non-MXene halide-terminated 2D materials, termed MXenoids. These surface modifications enable compositional and electronic structure engineering, introduce chiralmore » hybrid organic-inorganic structures, and photoluminescence ranging from near-IR to blue. This study highlights the avenue of surface chemistry-driven materials design, enhancing the functional capabilities of 2D materials.« less

Porous organic materials showcasing large framework dynamics present new paths for adsorption and separation with enhanced capacity and selectivity beyond the size-sieving limits, which is attributed to their guest-responsive sorption behaviors. Porous hydrogen-bonded crosslinked organic frameworks (H_COFs) are attractive for their remarkable ability to undergo guest-triggered expansion and contraction facilitated by their flexible covalent crosslinkages. However, the voids of H_COFs remain limited, which restrains the extent of the framework dynamics. Here in this work, we synthesized a series of H_COFs characterized by unprecedented size expansion capabilities induced by solvents. These H_COFs were constructed by isoreticularly co-crystallizing two complementary sets ofmore » hydrogen bonding building blocks to generate porous molecular crystals, which were crosslinked through thiol–ene/yne single-crystal-to-single-crystal transformations. The generated H_COFs exhibit enhanced chemical durability, high crystallinity, and extraordinary framework dynamics. For instance, H_COF-104 crystals featuring a pore diameter of 13.6 Å expanded in DMF to 300 ± 10% of their original lengths within just 1 min. This expansion allows the HCOFs to adsorb guest molecules that are significantly larger than the pore sizes of their crystalline states. Through methanol-induced contraction, these large guests were encapsulated in the fast-contracted H_COFs. These advancements in porous framework dynamics pave the way for new methods of encapsulating guests for targeted delivery.« less

¹ H{X} DE-RESPDOR pulse sequences enable the rapid detection of wideline solid-state nuclear magnetic resonance spectra of spin 3/2 half-integer quadrupolar nuclei.

Two-dimensional (2D) transition-metal carbides and nitrides (MXenes) combine the electronic and mechanical properties of 2D inorganic crystals with chemically modifiable surfaces, which provides an ideal platform for both fundamental and applied studies of interfaces. Good progress has been achieved in the functionalization of MXenes with small inorganic ligands, but relatively little work has been reported on the covalent bonding of various organic groups to MXene surfaces. Here we synthesize a family of hybrid MXenes (h-MXenes) that incorporate amido- and imido-bonding between organic and inorganic parts by reacting halogen-terminated MXenes with deprotonated organic amines. The resulting hybrid structures unite tailorability ofmore » organic molecules with electronic connectivity and other properties of inorganic 2D materials. Describing the structure of h-MXene necessitates the integration of concepts from coordination chemistry, self-assembled monolayers and surface science. The optical properties of h-MXenes reveal coherent coupling between the organic and inorganic constituents. Further, h-MXenes also exhibit superior stability against hydrolysis.« less

Iodine is widely used as an antimicrobial reagent for water disinfection in the wilderness and outer space, but residual iodine and iodide need to be removed for health reasons. Currently, it is challenging to remove low concentrations of iodine and iodide in water (~5 ppm). Furthermore, the remediation of iodine and iodide across a broad temperature range (up to 90 °C) has not previously been investigated. In this work, we report a nitrate dimer-directed synthesis of a single-crystalline ionic hydrogen-bonded crosslinked organic framework (HCOF-7). HCOF-7 removes iodine and iodide species in water efficiently through halogen bonding and anion exchange, reducingmore » the total iodine concentration to 0.22 ppm at room temperature. Packed HCOF-7 columns were employed for iodine/iodide breakthrough experiments between 23 and 90 °C, and large breakthrough volumes were recorded (≥18.3 L/g). Finally, the high iodine/iodide removal benchmarks recorded under practical conditions make HCOF-7 a promising adsorbent for water treatment.« less

Abstract Iodine is widely used as an antimicrobial reagent for water disinfection in the wilderness and outer space, but residual iodine and iodide need to be removed for health reasons. Currently, it is challenging to remove low concentrations of iodine and iodide in water (≈5 ppm). Furthermore, the remediation of iodine and iodide across a broad temperature range (up to 90 °C) has not previously been investigated. In this work, we report a nitrate dimer‐directed synthesis of a single‐crystalline ionic hydrogen‐bonded crosslinked organic framework (H _C OF‐7). H _C OF‐7 removes iodine and iodide species in water efficiently through halogen bonding andmore » anion exchange, reducing the total iodine concentration to 0.22 ppm at room temperature. Packed H _C OF‐7 columns were employed for iodine/iodide breakthrough experiments between 23 and 90 °C, and large breakthrough volumes were recorded (≥18.3 L g ⁻¹ ). The high iodine/iodide removal benchmarks recorded under practical conditions make H _C OF‐7 a promising adsorbent for water treatment.« less

We report heterobimetallic complexes have attracted much interest due to their broad range of structures and reactivities as well as unique catalytic abilities. Additionally, these complexes can be utilized as single-source precursors for the synthesis of binary intermetallic compounds. An example is the family of bis(pyridine-2-thiolato)dichloro-germanium and tin complexes of group 10 metals (Pd and Pt). The reactivity of these heterobimetallic complexes is highly tunable through substitution of the group 14 element and the neutral ligand bound to the transition metal. Here, we study the binding energies of three different phosphorous-based ligands, PR₃ (R = Bu, Ph, and OPh) bymore » density functional theory and restricted Hartree–Fock methods. The PR₃ ligand-binding energies follow the trend of PBu₃ > PPh₃ > P(OPh)₃, in agreement with their sigma-bonding ability. These results are confirmed by ligand exchange experiments monitored with ³¹P NMR spectroscopy, in which a weaker binding PR₃ ligand is replaced with a stronger one. Furthermore, we demonstrate that the heterobimetallic complexes are active catalysts in the Negishi coupling reaction, where stronger binding PR₃ ligands inhibit access to an active site at the metal center. Similar strategies could be applied to other complexes to better understand their ligand-binding energetics and predict their reactivity as both precursors and catalysts.« less

¹H{X} symmetry-based rotational echo double resonance pulse sequences (S-REDOR) and symmetry-based rotational echo saturation pulse double resonance (S-RESPDOR) solid-state NMR experiments have found widespread application for ¹H detected measurements of difference NMR spectra, dipolar coupling constants, and internuclear distances under conditions of fast magic angle spinning (MAS). In these experiments the supercycled $$\text{R4}^2_1 (\text{SR4}^2_1)$$ symmetry-based recoupling pulse sequence is typically applied to the ¹H spins to reintroduce heteronuclear dipolar couplings. However, the timing of $$\text{SR4}^2_1$$ and other symmetry-based pulse sequences must be precisely synchronized with the rotation of the sample, otherwise, the evolution of ¹H CSA and other interactions willmore » not be properly refocused. For this reason, significant distortions are often observed in experimental dipolar dephasing difference curves obtained with S-REDOR or S-RESPDOR pulse sequences. Here we introduce a family of double echo (DE) S-REDOR/S-RESPDOR pulse sequences that function in an analogous manner to the recently introduced $$t_1$$-noise eliminated (TONE) family of dipolar heteronuclear multiple quantum coherence (D-HMQC) pulse sequences. Through numerical simulations and experiments the DE S-REDOR/S-RESPDOR sequences are shown to provide dephasing difference curves similar to those obtained with S-REDOR/S-RESPDOR. However, the DE sequences are more robust to the deviations of the MAS frequency from the ideal value that occurs during typical solid-state NMR experiments. In this work, the DE sequences are shown to provide more reliable ¹H detected dipolar dephasing difference curves for nuclei such as ¹⁵N (with isotopic labelling), ¹⁸³W and ³⁵Cl. The double echo sequences are therefore recommended to be used in place of conventional S-REDOR/S-RESPDOR sequences for measurement of weak dipolar coupling constants and long-range distances.« less