Insights into the mechanism of energy transfer with poly(heptazine imide)s in deoximation reaction

Following our previous studies on potassium poly(heptazine imide) (K-PHI) – catalyzed photooxidative [3+2] aldoxime-to-nitrile addition to form 1,2,4-oxadiazoles, we discovered that electron-rich oximes yield the parent aldehydes instead of target products. In this work, the mechanism of this singlet oxygen-mediated deoximation process was established using a series of control reactions and spectroscopic measurements such as steady-state and time-resolved fluorescence quenching experiments. Additionally, singlet-triplet energy gap value was obtained for K-PHI in suspension, and the reaction scope was broadened to include ketoximes

Multisite PCET with photocharged carbon nitride in dark

A combination of photochemistry and proton coupled electron transfer (PCET) is a primary strategy employed by biochemical systems and synthetic chemistry to enable uphill reactions under mild conditions. Degenerate nanometer-sized n-type semiconductor nanoparticles (SCNPs) with the Fermi level above the bottom of the conduction band are strongly reducing and act more like metals than semiconductors. Application of the degenerate SCNPs is limited to few examples. Herein, we load microporous potassium poly(heptazine imide) (K-PHI) nanoparticles with electrons (e–) and charge balancing protons (H+) in an illumination phase using sacrificial agents. e–/H+ in the K-PHI nanoparticles are weakly bound and therefore could be used in a range of PCET reactions in dark, such as generation of aryl radicals from aryl halides, ketyl radicals from ketones, and 6e–/6H+ reduction of nitrobenzene to aniline. The integration of several features that until now were intrinsic for plants and natural photosynthesis into a transition metal free nanomaterial composed of abundant elements (C, N, and K) offers a powerful tool for synthetic organic chemistry

Workplace flexibility across the lifespan

As demographic changes impact the workplace, governments, organizations and workers are looking for ways to sustain optimal working lives at higher ages. Workplace flexibility has been introduced as a potential way workers can have more satisfying working lives until their retirement ages. This paper presents a critical review of the literature on workplace flexibility across the lifespan. It discusses how flexibility has been conceptualized across different disciplines, and postulates a definition that captures the joint roles of employer and employee in negotiating workplace flexibility that contributes to both employee and organization benefits. Moreover, it reviews how flexibility has been theorized and investigated in relation to older workers. The paper ends with a future research agenda for advancing understanding of how workplace flexibility may enhance working experiences of older workers, and in particular focuses on the critical investigation of uses of flexibility in relation to older workers

A cross-national study on the antecedents of work–life balance from the fit and balance perspective

Drawing on the perceived work–family fit and balance perspective, this study investigates demands and resources as antecedents of work–life balance (WLB) across four countries (New Zealand, France, Italy and Spain), so as to provide empirical cross-national evidence. Using structural equation modelling analysis on a sample of 870 full time employees, we found that work demands, hours worked and family demands were negatively related to WLB, while job autonomy and supervisor support were positively related to WLB. We also found evidence that resources (job autonomy and supervisor support) moderated the relationships between demands and work–life balance, with high resources consistently buffering any detrimental influence of demands on WLB. Furthermore, our study identified additional predictors of WLB that were unique to some national contexts. For example, in France and Italy, overtime hours worked were negatively associated with WLB, while parental status was positively associated with WLB. Overall, the implications for theory and practice are discussed.Peer ReviewedPostprint (author's final draft

Socioeconomic mobility and talent utilization of workers from poorer backgrounds: The overlooked importance of within-organization dynamics

Socioeconomic mobility, or the ability of individuals to improve their socioeconomic standing through merit-based contributions, is a fundamental ideal of modern societies. The key focus of societal efforts to ensure socioeconomic mobility has been on the provision of educational opportunities. We review evidence that even with the same education and job opportunities, being born into a poorer family undermines socioeconomic mobility due to processes occurring within organizations. The burden of poorer background might, ceteris paribus, be economically comparable to the gender gap. We argue that in the societal and scientific effort to promote socioeconomic mobility, the key context in which mobility is supposed to happen—organizations—as well as the key part of the life of people striving toward socioeconomic advancement—that as working adults—have been overlooked. We integrate the organizational literature pointing to key within-organizational processes impacting objective (socioeconomic) success with research, some emergent in organizational sciences and some disciplinary, on when, why, and how people from poorer backgrounds behave or are treated by others in the relevant situations. Integrating these literatures generates a novel and useful framework for identifying issues people born into poorer families face as employees, systematizes extant evidence and makes it more accessible to organizational scientists, and allows us to lay the agenda for future organizational scholarshi

Kalium‐Polyheptazinimid: Ein übergangsmetallfreier Festkörper‐Triplett‐Sensibilisator in Kaskadenenergietransfer und [3+2]‐Cycloadditionen

Polymeric carbon nitride materials have been successfully used in numerous light-to-energy conversion applications ranging from photocatalysis to optoelectronics. For a new application and modelling, we first refined the crystal structure of potassium poly(heptazine imide) (K-PHI) – a benchmark carbon nitride material in photocatalysis – by means of X-ray powder diffraction and transmission electron microscopy. Using the crystal structure of K-PHI, periodic DFT calculations were performed to calculate the density-of-states and localize intra band states (IBS). IBS were found to be responsible for the enhanced K-PHI absorption in the near IR region, to serve as electron traps, and to be useful in energy transfer reactions. Once excited with visible light, carbon nitrides, beside the direct recombination, can also undergo singlet-triplet intersystem crossing. We utilized the K-PHI centered triplet excited states to trigger a cascade of energy transfer reactions and, in turn, to sensitize, for example, singlet oxygen (1O2) as a starting point to synthesis up to 25 different N-rich heterocycles