Incorporation of secondary metal ions into heterobimetallic complexes has emerged as an attractive strategy for rational tuning of compounds’ properties and reactivity, but direct solution-phase spectroscopic interrogation of tuning effects has received less attention than it deserves. Here, we report assembly and study of a series of heterobimetallic complexes containing the vanadyl ion, [VO]2+, paired with mono-valent cations (Cs+, Rb+, K+, Na+, and Li+) or a di-valent cation (Ca2+). These complexes, which can be isolated in pure form or generated in situ from a common monometallic vanadyl-containing precursor, enable experimental spectroscopic quantification of the influence of the incorporated cations on the properties of the vanadyl moiety. The data reveal systematic shifts in the V–O stretching frequency and isotropic hyperfine coupling constant for the vanadium center in the complexes. These shifts can be interpreted as charge density effects parametrized through the Lewis acidities of the cations, suggesting broad potential for the vanadyl ion to serve as a spectroscopic probe in multimetallic species.

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BACKGROUND: People with traumatic brain injury (TBI) can lack awareness of their own emotions and often have problems with emotion dysregulation, affective disorders, and empathy deficits. These impairments are known to impact psychosocial behaviors and may contribute to the burden experienced by care partners of individuals with TBI. OBJECTIVE: To examine the associations of emotional awareness, emotional functioning, and empathy among participants with TBI with care partner burden. METHOD: This multisite, cross-sectional, observational study used data from 90 dyads (participants with TBI and their care partner) 1-year post-injury. Participants with TBI completed the Difficulty with Emotional Regulation Scale (DERS; Awareness, Clarity, Goals, Impulse, Nonacceptance, and Strategies subscales); PTSD Checklist-Civilian Version; NIH Toolbox Anger-Affect, Hostility and Aggression Subdomains; PHQ-9; GAD-7; and the Interpersonal Reactivity Index (empathic concern and perspective taking subscales). Care partners completed the Zarit Burden Inventory (ZBI) and provided demographic information. RESULTS: Care partners were predominately female (77%), and most were either a spouse/partner (55.2%) or parent (34.4%). In an unadjusted model that included assessments of emotional awareness, emotional functioning, and empathy of the participant with TBI, the DERS-Awareness and NIH- Hostility subscales accounted for a significant amount of variance associated with care partner burden. These findings persisted after adjusting for care partner age, relationship, education, and the functional status of the participant with TBI (β= 0.493 and β= 0.328, respectively). CONCLUSION: These findings suggest that that high levels of hostility and low emotional self-awareness can significantly affect the burden felt by TBI care partners.

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