Symmetrical Analogues Research Articles

Extraction of Lanthanides(III) from Nitric Acid Solutions with N,N′-dimethyl-N,N′-dicyclohexyldiglycolamide into Bis(trifluoromethylsulfonyl)imide-Based Ionic Liquids and Their Mixtures with Molecular Organic Diluents

The extraction of lanthanides(III) from aqueous nitric acid solutions with novel unsymmetrical diglycolamide extactant, N,N′-dimethyl-N,N′-dicyclohexyldiglycolamide (DMDCHDGA) into bis(trifluoromethylsulfoyl)imide-based ionic liquids (ILs), namely 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C4mim][Tf2N]), 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C8mim][Tf2N]), benzyltriethylammonium bis(trifluoromethylsulfonyl)imide ([N222Bn][Tf2N]) methyltrioctylammonium bis(trifluoromethylsulfonyl)imide ([N1888][Tf2N]), and their mixtures with molecular organic diluent 1,2-dichloroethane (DCE), is studied. DMDCHDGA has been shown to interact with components of the IL [C4mim][Tf2N]. The effect of HNO3 concentration in the aqueous phase on the extraction of Ln(III) ions is studied. The stoichiometry of the extracted complexes is determined, and the mechanism of Ln(III) extraction in a system with [C4mim][Tf2N] is discussed. It is shown that the efficiency and intragroup selectivity of the extraction of Ln(III) ions with DMDCHDGA into [C4mim][Tf2N] is significantly higher than when using its symmetric analog TODGA.

A density functional theory study of a series of symmetric dibenzylideneacetone analogues as potential chemical UV-filters

The aim of this research was to provide valuable insights on symmetrical α,β-unsaturated ketones as potential chemical ultraviolet (UV) filters from experimental data and theoretical aspects. Towards this end, density functional theory (DFT/B3LYP) calculations on a series of symmetrical α,β-unsaturated ketones, (1E,4E)-1,5-bis[4-(R)phenyl]penta-1,4-diene-3-one (R = methylthio, 1; R = dimethylamino, 2; R = ethyl, 3), were performed to determine the effect of different electron-donating substituents on their stability when exposed to solar UV radiation. Their molecular structures, and UV–visible, infrared (IR) and NMR (1H and 13C) spectra were theoretically obtained from their optimized geometries with the B3LYP/6–311++ G (d, p) basis set and were compared with the experimental results. Conformational analysis was performed and the most stable conformer of each compound was identified as the trans-trans conformer, which was further supported by experimental NMR data. The UV spectra and effect of solvent polarity and proticity were studied by the time-dependent-DFT (TD-DFT) approach with the B3LYP/6–311++G (d, p) level of theory. Furthermore, various molecular parameters like dipole moment, frontier molecular orbital (FMO) energies, ΔEHOMO-LUMO gap, lifetime of the first excited state (τ), global chemical reactivity descriptors, and natural bond orbital analysis were predicted at the same level of theory and compared with the experimental data. Inspection of the active FMOs revealed the photoinstability trends of 1 and 3 under UV irradiation. However, introducing a -N(CH3)2 substituent to 2 at the para-position improves its photostability towards simulated solar UV radiation. Thus, compound 2 has the potential to provide efficient broad-spectrum protection against UV radiation. This work has shown that molecular modelling strategies can assist to rationalize experimental findings and also support the identification of photoproducts of 1 and 3.

Mix and Match Tuning of the Conformational and Multistate Redox Switching Properties of an Overcrowded Alkene.

Overcrowded alkenes have received considerable attention as versatile structural motifs in a range of optical switches and light-driven unidirectional motors. In contrast, their actuation by electrochemical stimuli remains underexplored, even though this alternative energy input may be preferred in various applications and enables additional control over molecular switching states and properties. While symmetric bistricyclic overcrowded enes (BAEs) containing two identical halves based on either thioxanthene (TX) or acridine (Acr) motifs are known to be reversible conformational redox switches, their redox potentials are generally too high or low, respectively, thereby preventing wider applications. Herein, we demonstrate that the "mixed" TX-Acr switch possesses redox properties that lie between those of its parent symmetric analogs, enabling interconversion between three stable redox and conformational states at mild potentials. This includes the neutral anti-folded, the dicationic orthogonal, and a unique twisted monoradical cation state, the latter of which is only accessible in the case of the mixed TX-Acr switch and in a pathway-dependent manner. Consequently, with this multistate redox switch, a myriad of molecular properties, including geometry, polarity, absorbance, and fluorescence, can be modulated with high fidelity and reversibility between three distinct stable states. More generally, this study highlights the versatility of the "mix and match" approach in rationally designing redox switches with specific (redox) properties, which in turn is expected to enable a myriad of applications ranging from molecular logic and memory to actuators and energy storage systems.

A non-symmetric room-temperature tristriazolotriazine liquid crystal

Tristriazolotriazine (TTT) has emerged as an easily accessible electron-deficient heterocyclic core for discotic liquid crystals (LCs). Materials that are liquid-crystalline at room temperature, i.e., do not crystallize in ambient conditions, are of particular interest when the LC state is prone to offer advantages in optoelectronic devices, e.g., for anisotropic charge or exciton transport, or anisotropic light emission. However, there has been no report of non-symmetric TTT LCs, i.e., with unequal arms. Here, we report two non-symmetric compounds derived from the TTT core. Their non-symmetry, combined with a high number of peripheral alkyl chains, is found to promote Colh mesomorphism over a broad temperature range including room temperature. The non-symmetry also induces an increase in the emission quantum yield, compared to symmetric analogs.

Unsymmetric Co-Facial "Salixpyrrole" Hydrogen Evolution Catalysts: Two Metals are Better than One.

Designing ligand architectures that can mimic enzyme active sites is a promising approach for developing efficient small molecule activation catalysts for sustainable energy applications. Some key design features include chemically distinct binding pockets for multiple metal centers and a three-dimensional structure that controls the positioning of catalytic sites. With these principles in mind, mono- and bimetallic unsymmetric cofacial palladium complexes, 2 and 3, respectively, bearing ligands with calixpyrrole and salen coordination sites, or "salixpyrrole" ligands, are reported. These species were accessed in a straightforward Schiff-base reaction with appreciable yields. In addition, both 2 and 3 were found to be active hydrogen evolution electrocatalysts using para-toluenesulfonic acid monohydrate as the proton source. The two salixpyrrole species displayed different mechanisms of action, with 2 showing a second-order dependence on acid concentration, whereas 3 exhibited a first-order dependence. Moreover, the bimetallic catalyst was significantly more efficient, with higher turnover frequencies, 4640 s-1 vs 1680 s-1 for 2, and lower overpotentials, 0.39 V vs 0.69 V for 2. The results reported herein provide proof-of-concept that bimetallic catalysts with chemically distinct binding sites demonstrate enhanced catalytic properties in comparison to monometallic or symmetric analogues.

Asymmetrical Diketopyrrolopyrrole Derivatives with Improved Solubility and Balanced Charge Transport Properties.

The diketopyrrolopyrrole (DPP) unit represents one of the building blocks more widely employed in the field of organic electronics; in most of the reported DPP-based small molecules, this unit represents the electron acceptor core symmetrically coupled to donor moieties, and the solubility is guaranteed by functionalizing lactamic nitrogens with long and branched alkyl tails. In this paper, we explored the possibility of modulating the solubility by realizing asymmetric DPP derivatives, where the molecular structure is extended in just one direction. Four novel derivatives have been prepared, characterized by a common dithyenil-DPP fragment and functionalized on one side by a thiophene unit linked to different auxiliary electron acceptor groups. As compared to previously reported symmetric analogs, the novel dyes showed an increased solubility in chloroform and proved to be soluble in THF as well. The novel dyes underwent a thorough optical and electrochemical characterization. Electronic properties were studied at the DFT levels. All the dyes were used as active layers in organic field effect transistors, showing balanced charge transport properties.

Optimizing Molecular Crystallinity and Suppressing Electron-Phonon Coupling in Completely Non-Fused Ring Electron Acceptors for Organic Solar Cells.

High open-circuit voltage (Voc) organic solar cells (OSCs) have received increasing attention because of their promising application in tandem devices and indoor photovoltaics. However, the lack of a precise correlation between molecular structure and stacking behaviors of wide band gap electron acceptors has greatly limited its development. Here, we adopted an asymmetric halogenation strategy (AHS) and synthesized two completely non-fused ring electron acceptors (NFREAs), HF-BTA33 and HCl-BTA33. The results show that AHS significantly enhances the molecular dipoles and suppresses electron-phonon coupling, resulting in enhanced intramolecular/intermolecular interactions and decreased nonradiative decay. As a result, PTQ10 : HF-BTA33 realizes a power conversion efficiency (PCE) of 11.42 % with a Voc of 1.232 V, higher than that of symmetric analogue F-BTA33 (PCE=10.02 %, Voc=1.197 V). Notably, PTQ10 : HCl-BTA33 achieves the highest PCE of 12.54 % with a Voc of 1.201 V due to the long-range ordered π-π packing and enhanced surface electrostatic interactions thereby facilitating exciton dissociation and charge transport. This work not only proves that asymmetric halogenation of completely NFREAs is a simple and effective strategy for achieving both high PCE and Voc, but also provides deeper insights for the precise molecular design of low cost completely NFREAs.

Optimizing Molecular Crystallinity and Suppressing Electron‐Phonon Coupling in Completely Non‐Fused Ring Electron Acceptors for Organic Solar Cells

AbstractHigh open‐circuit voltage (Voc) organic solar cells (OSCs) have received increasing attention because of their promising application in tandem devices and indoor photovoltaics. However, the lack of a precise correlation between molecular structure and stacking behaviors of wide band gap electron acceptors has greatly limited its development. Here, we adopted an asymmetric halogenation strategy (AHS) and synthesized two completely non‐fused ring electron acceptors (NFREAs), HF‐BTA33 and HCl‐BTA33. The results show that AHS significantly enhances the molecular dipoles and suppresses electron‐phonon coupling, resulting in enhanced intramolecular/intermolecular interactions and decreased nonradiative decay. As a result, PTQ10 : HF‐BTA33 realizes a power conversion efficiency (PCE) of 11.42 % with a Voc of 1.232 V, higher than that of symmetric analogue F‐BTA33 (PCE=10.02 %, Voc=1.197 V). Notably, PTQ10 : HCl‐BTA33 achieves the highest PCE of 12.54 % with a Voc of 1.201 V due to the long‐range ordered π–π packing and enhanced surface electrostatic interactions thereby facilitating exciton dissociation and charge transport. This work not only proves that asymmetric halogenation of completely NFREAs is a simple and effective strategy for achieving both high PCE and Voc, but also provides deeper insights for the precise molecular design of low cost completely NFREAs.

Synergetic optimizing quinoxaline and selenophene substitution in non-fullerene acceptors for efficient organic solar cells

Selenophene-fused non-fullerene acceptors (Se-NFAs) usually exhibited improved short circuit current density (JSC) in organic solar cells, while acceptors bearing quinoxaline (Qx) unit as the central core could achieve enhanced open circuit voltage (VOC). Herein, we incorporated the advantages of the above two strategies and synthesized four nonfullerene acceptors (Qx-Se-NFAs), including Qx-Se-F, Qx-Se-Cl, p-2FQx-Se-F, and p-2FQx-Se-Cl. Compared with CH1007 (the symmetrical selenium analog of Y6), the four acceptors-based devices showed evidently improved VOC and fill factor (FF) with well-maintained JSC, achieving excellent power conversion efficiency (PCE). Qx-Se-NFAs-based devices with the fluorinated terminal group exhibit evidently advantages on VOC and FF compared with the chlorinated terminal group due to the up-shifted LUMO energy level and optimized blend film. In addition, the acceptors with fluorination on the central core could further endow device with improved carrier properties and film morphology. Consequently, the device based on Qx-Se-F exhibited the highest VOC of 0.867 V among the reported PM6:Se-NFA systems. The p-2FQx-Se-F-based device yielded a champion PCE of 18.67% by using 2PACz as the hole transport layer, which is the highest PCE in the reported Se-NFAs among the single-junction binary OSCs. This work demonstrated a promising strategy that could better trade-off JSC, FF, and VOC in Se-NFAs.

Synergistically Modulating Conductive Filaments in Ion-Based Memristors for Enhanced Analog In-Memory Computing.

Memristors offer a promising solution to address the performance and energy challenges faced by conventional von Neumann computer systems. Yet, stochastic ion migration in conductive filament often leads to an undesired performance tradeoff between memory window, retention, and endurance. Herein, a robust memristor based on oxygen-rich SnO2 nanoflowers switching medium, enabled by seed-mediated wet chemistry, to overcome the ion migration issue for enhanced analog in-memory computing is reported. Notably, the interplay between the oxygen vacancy (Vo) and Ag ions (Ag+) in the Ag/SnO2/p++-Si memristor can efficiently modulate the formation and abruption of conductive filaments, thereby resulting in a high on/off ratio (>106), long memory retention (10-year extrapolation), and low switching variability (SV = 6.85%). Multiple synaptic functions, such as paired-pulse facilitation, long-term potentiation/depression, and spike-time dependent plasticity, are demonstrated. Finally, facilitated by the symmetric analog weight updating and multiple conductance states, a high image recognition accuracy of ≥ 91.39% is achieved, substantiating its feasibility for analog in-memory computing. This study highlights the significance of synergistically modulating conductive filaments in optimizing performance trade-offs, balancing memory window, retention, and endurance, which demonstrates techniques for regulating ion migration, rendering them a promising approach for enabling cutting-edge neuromorphic applications.

New asymmetric tetradentate phenanthroline chelators with pyrazole and amide groups for complexation and solvent extraction of Ln(III)/Am(III).

To tune the complexation and solvent extraction performance of the ligands with a 1,10-phenanthroline core for trivalent actinides (An3+) and lanthanides (Ln3+), we synthesized two new asymmetric tetradentate ligands with pyrazole and amide groups, i.e., L1 (N,N-diethyl-9-(5-ethyl-1H-pyrazol-3-yl)-1,10-phenanthroline-2-carboxamide) and its analogue L2 with longer alkyl chains (N,N-dihexyl). The complexation of the ligands with Ln3+ was confirmed by 1H NMR titration and X-ray crystallography, and stability constants were measured in methanol by spectrophotometric titration. The asymmetric ligands exhibited an improved performance in terms of selective solvent extraction of Am3+ over Eu3+ in strongly acidic solutions compared to their symmetric analogues. The improved selectivity of the asymmetric ligands was interpreted theoretically by density functional theory simulations. This study implies that combining different functional groups to construct asymmetric ligands may be an efficient way to tune ligand performance with regard to An3+ separation from Ln3+.

Mechanistic insights into nitric oxide generation from nitrite via O-atom transfer in the unsymmetrical β-diketiminato copper(II) nitrite complex.

In this study, we employed DFT calculations to elucidate the mechanism of NO generation from nitrite via PPh3-induced oxygen atom transfer (OAT) in the unsymmetrical β-diketiminato copper(II), LCuIIONO. We discovered that the OAT process involves the cooperation of two PPh3 ligands and follows the mechanism distinct from that of the symmetrical β-diketiminato analogue. The ΔG‡ value, calculated to be 34.8 kcal mol-1, closely matches experimental data. The finding is further supported by analyzing the OAT product yields with varying equivalents of PPh3. The penta-coordinated species 5a, with PPh3 occupying the axial site, forms in the final stage of the OAT process. The isomerization of 5a and the decoordination of the hemilabile pyridyl arm synergistically reduce Cu(II) to Cu(I), facilitating NO release from the Cu(I) centre. These computational results provide valuable insights for the ligand design for PPh3-induced OAT reactions to produce NO in Cu(II) nitrite systems.

Synthesis of (thio)alkyloxy-substituted perfluorinated terphenyl derivatives: Optical properties, molecular docking and antioxidant activity

Nucleophilic aromatic substitution (SNAr) has been known to be a strongly para-selective reaction for various multifunctional perfluoroaryls. In the current study, we report the application of SNAr chemistry to synthesize different derivatives of optically active symmetrical and asymmetrical perfluorinated fluoroterphenyl analogues. The synthesis procedures include a Cu-assisted decarboxylation of perfluorinated fluorobenzoate derivatives and SNAr reaction to produce (thio)alkyloxy-substituted perfluorinated fluoroterphenyls in respectable yield and superb purity starting from the potassium salt of perfluorobenzoate and aryl iodide. The synthesized adducts were inspected by FT-IR and 1H/13C/19F NMR spectroscopy. The optical properties of the synthesized perfluorinated adducts were explored. The absorption and fluorescence spectra showed solvatochromic properties. The DPPH procedure was utilized to inspect the synthesized perfluoroterphenyl analogues for their antioxidant activity. The results demonstrated that the perfluoroterphenyl adducts with asymmetrical hydrocarbon chain exhibited maximum efficiency over an IC50 =10.25±0.24 µg/mL. Moreover, the perfluoroterphenyl adducts were employed in molecular docking using (PDB: 5IKQ) protein.

High‐Performance Memristors Based on Few‐Layer Manganese Phosphorus Trisulfide for Neuromorphic Computing

AbstractWhile transition‐metal thiophosphate (MPX3) materials have been a subject of extensive research in recent years, experimental studies on MPX3‐based memristors are still in their early stages, with device performance being less than ideal. Here, the successful fabrication of high‐yield, high‐performance, and uniform memristors are demonstrated to possess desired characteristics for neuromorphic computing using a single‐crystalline few‐layered manganese phosphorus trisulfide (MnPS3) as a resistive switching medium. The Ti/MnPS3/Au memristor exhibits small switching voltage (<1 V), long memory retention (104 s), fast switching speed (≈20 ns), high On/Off ratio (nearly two orders of magnitude), and simultaneously achieves emulation of synaptic weight plasticity. The microscopic investigation of the structural and chemical characteristics of the few‐layer MnPS3 reveals the presence of structural defects and residual Ti throughout the stacked layer following the application of voltage, which contributes to the uniformity of switching with a low set voltage. With highly linear and symmetric analog weight updates coupled with the capability of accurate decimal arithmetic operations, a high accuracy of 95.15% in supervised learning using the MNIST handwritten recognition dataset is achieved in the artificial neural network. Furthermore, convolutional image processing can be implemented using hardware multiply‐and‐accumulate operation in an experimental memristor crossbar array.

Enhancing Photovoltaic Performance of Nonfused‐Ring Electron Acceptors via Asymmetric End‐Group Engineering and Noncovalently Conformational Locks

Comprehensive SummaryBy employing the asymmetric end‐group engineering, an asymmetric nonfused‐ring electron acceptor (NFREA) was designed and synthesized. Compared with the symmetric analogs (NoCA‐17 and NoCA‐18), NoCA‐19 possesses broader light absorption range, more coplanar π‐conjugated backbone, and appropriate crystallinity according to the experimental and theoretical results. The organic solar cells based on J52:NoCA‐19 exhibited a power conversion efficiency as high as 12.26%, which is much higher than those of J52:NoCA‐17 (9.50%) and J52:NoCA‐18 (11.77%), mainly due to more efficient exciton dissociation, better and balanced charge mobility, suppressed recombination loss, shorter charge extraction time, longer charge carrier lifetimes, and more favorable blend film morphology. These findings demonstrate the great potential of asymmetric end‐group engineering in exploring low‐cost and high‐performance NFREAs.

Understanding the Impact of Symmetrical Substitution on the Photodynamics of Sinapate Esters Using Gas-Phase Ultrafast Spectroscopy.

Two model biomimetic systems, ethyl sinapate (ES) and its symmetrical analogue, diethyl 2-(4-hydroxy-3,5-dimethoxybenzylidene)malonate (or diethyl sinapate, DES), are stripped to their core fundamentals through gas-phase spectroscopy to understand the underlying photophysics of photothermal materials. Following photoexcitation to the optically bright S1(ππ*) state, DES is found to repopulate the electronic ground state over 3 orders of magnitude quicker than its nonsymmetrical counterpart, ES. Our XMS-CASPT2 calculations shed light on the experimental results, revealing crucial differences in the potential energy surfaces and conical intersection topography between ES and DES. From this work, a peaked conical intersection, seen for DES, shows vital importance for the nonradiative ground-state recovery of photothermal materials. This fundamental comparative study highlights the potential impact that symmetrical substitution can have on the photodynamics of sinapate esters, providing a blueprint for future advancement in photothermal technology.

A Smoothing Method for Sparse Programs by Symmetric Cone Constrained Generalized Equations

In this paper, we consider a sparse program with symmetric cone constrained parameterized generalized equations (SPSCC). Such a problem is a symmetric cone analogue with vector optimization, and we aim to provide a smoothing framework for dealing with SPSCC that includes classical complementarity problems with the nonnegative cone, the semidefinite cone and the second-order cone. An effective approximation is given and we focus on solving the perturbation problem. The necessary optimality conditions, which are reformulated as a system of nonsmooth equations, and the second-order sufficient conditions are proposed. Under mild conditions, a smoothing Newton approach is used to solve these nonsmooth equations. Under second-order sufficient conditions, strong BD-regularity at a solution point can be satisfied. An inverse linear program is provided and discussed as an illustrative example, which verified the efficiency of the proposed algorithm.

Platinum(II) Complexes of Nonsymmetrical NCN-Coordinating Ligands: Unimolecular and Excimeric Luminescence Properties and Comparison with Symmetrical Analogues.

A series of seven new platinum(II) complexes PtLnCl have been prepared, where Ln is an NCN-coordinating ligand comprising a benzene ring 1,3-disubstituted with two different azaheterocycles. In PtL1-5Cl, one heterocycle is a simple pyridine ring, while the other is an isoquinoline, a quinoline, a pyrimidine (L1, L2, L3), or a p-CF3- or p-OMe-substituted pyridine (L4 and L5). PtL6Cl incorporates both a p-CF3 and a p-OMe-substituted pyridine. The synthesis of the requisite proligands HLn is achieved using Pd-catalyzed cross-coupling methodology. The molecular structures of six of the Pt(II) complexes have been determined by X-ray diffraction. All the complexes are brightly luminescent in deoxygenated solution at room temperature. The absorption and emission properties are compared with those of the corresponding symmetrical complexes featuring two identical heterocycles, PtLnsymCl, and of the parent Pt(dpyb)Cl containing two unsubstituted pyridines [dpybH = 1,3-di(2-pyridyl)benzene]. While the absorption spectra of the nonsymmetrical complexes show features of both PtLnsymCl and Pt(dpyb)Cl, the emission generally resembles that of whichever of the corresponding symmetrical complexes has the lower-energy emission. PtL1Cl differs in that─at room temperature but not at 77 K─it displays emission bands that can be attributed to excited states involving both the pyridine and the isoquinoline rings, despite the latter being unequivocally lower in energy. This unusual behavior is attributed to thermally activated repopulation of the former excited state from the latter, facilitated by the very long-lived nature of the isoquinoline-based excited state. At elevated concentrations, all the complexes show an additional red-shifted emission band attributable to excimers. For PtL1Cl, the excimer strikingly dominates the emission spectra at all but the lowest concentrations (<10-5 M). Trends in the energies of the excimers and their propensity to form are compared with those of the symmetrical analogues.

Cu(I)-catalyzed Synthesis of Symmetrical Perfluoroterphenyl Analogues; Fluorescence, Antioxidant and Molecular Docking studies.

Pentafluoroaryl analogues have been found to exhibit para specific nucleophilic aromatic substitution (SN Ar). Herein, we describe the use of SN Ar chemistry to create luminous perfluorinated symmetrical terphenyls. Both of SN Ar chemistry and Cu(I)-catalyzed decarboxylative cross-coupling were applied for the synthesis of those perfluorinated symmetrical terphenyls in high yields from the corresponding derivatives of aryl iodide and potassium salt of fluorobenzoate. A series of perfluorinated symmetrical terphenyls with different para alkoxy chains were synthesized. The synthesized perfluorinated terphenyl adducts were confirmed via elemental analysis, FT-IR, 1 H/13 C NMR, and 19 F NMR spectra. The absorbance and fluorescence spectra showed solvatochromic activities. The new synthesized fluoroterphenyl hybrids were screened against antioxidant inspection over DPPH performance, in assessment to Vitamin C and BHT as standard drugs exposed that fluoroterphenyl hybrid covering decyl hydrocarbons exhibited highest effectiveness through IC50 values 21.74 μg/mL. Additionally, molecular docking procedures of the synthesized fluoro-terphenyl hybrids were employed by using (PDB ID: 5IKQ) protein. The docking simulation was displayed convenient and recognized findings with the antioxidant examination.

Grothendieck-to-Lascoux expansions

We establish the conjecture of Reiner and Yong for an explicit combinatorial formula for the expansion of a Grothendieck polynomial into the basis of Lascoux polynomials. This expansion is a subtle refinement of its symmetric function version due to Buch, Kresch, Shimozono, Tamvakis, and Yong, which gives the expansion of stable Grothendieck polynomials indexed by permutations into Grassmannian stable Grothendieck polynomials. Our expansion is the K K -theoretic analogue of that of a Schubert polynomial into Demazure characters, whose symmetric analogue is the expansion of a Stanley symmetric function into Schur functions. Our expansions extend to flagged Grothendieck polynomials.