New Therapy for a New Normal: Comparing Telehealth and in-Person Time-Limited Parent-Child Interaction Therapy.

Telehealth treatment for child disruptive behavior has the potential to overcome multiple barriers to access (e.g., transportation, therapist availability). Traditional Parent-Child Interaction Therapy (PCIT) has demonstrated efficacy via telehealth in randomized controlled trials. The current study extends this research by examining community-based effectiveness of time-limited (i.e., 18 week) telehealth PCIT, comparing intake and posttreatment child behavior and caregiver skills for both telehealth and in-person PCIT. Participants included predominantly racially, ethnically, linguistically, and socioeconomically diverse children aged 2 to 8 years, and their caregivers. Dyads (N = 380) received either telehealth (IPCIT) or in-person PCIT.Propensity score analyses were conducted to address potential selection bias due to the nonrandomized sample. Regression analyses revealed no difference between IPCIT and in-person treatment for child disruptive behaviors or compliance outcomes. However, caregivers who received IPCIT demonstrated fewer positive statements and greater corrective/directive statements at posttreatment than caregivers who received in-person treatment.This research demonstrated that time-limited IPCIT can effectively improve child disruptive behavior among a socioeconomically, linguistically, and culturally diverse population, and represents the largest sample to date demonstrating the effectiveness of PCIT via telehealth. Future research is warranted to document intervention sustainability on a more system-wide level, and balance prioritizing caregiver skill acquisition over family-derived treatment goals.

Electronic Structures and Photoredox Chemistry of Tungsten(0) Arylisocyanides.

ConspectusThe high energy barriers associated with the reaction chemistry of inert substrates can be overcome by employing redox-active photocatalysts. Research in this area has grown exponentially over the past decade, as transition metal photosensitizers have been shown to mediate challenging organic transformations. Critical for the advancement of photoredox catalysis is the discovery, development, and study of complexes based on earth-abundant metals that can replace and/or complement established noble-metal-based photosensitizers.Recent work has focused on redox-active complexes of 3d metals, as photosensitizers containing these metals most likely would be scalable. Although low lying spin doublet ("spin flip") excited states of chromium(III) and metal-to-ligand charge transfer (MLCT) excited states of copper(I) have relatively long lifetimes, the electronic excited states of many other 3d metal complexes fall on dissociative potential energy surfaces, owing to the population of highly energetic σ-antibonding orbitals. Indeed, we and other investigators have shown that low lying spin singlet and triplet excited states of robust closed-shell metal complexes are too short-lived at room temperature to engage in bimolecular reactions in solutions. In principle, this problem could be overcome by designing and constructing 3d metal complexes containing strong field π-acceptor ligands, where thermally equilibrated MLCT or intraligand charge transfer excited states might fall well below the upper surfaces of dissociative 3d-3d states. Notably, such design elements have been exploited by investigators in very recent work on redox-active iron(II) systems. Another approach, one we have actively pursued, is to design and construct closed-shell complexes of earth-abundant 5d metals containing very strong π-acceptor ligands, where vertical excitation of 5d-5d excited states at the ground state geometry would require energies far above minima in the potential surfaces of MLCT excited states. As this requirement is met by tungsten(0) arylisocyanides, these complexes have been the focus of our work aimed at the development of robust redox-active photosensitizers.In the following Account, we review recent work on homoleptic tungsten(0) arylisocyanides. Originally reported by our group 45 years ago, W(CNAr)6 complexes have exceptionally large one- and two-photon absorption cross-sections. One- or two-photon excitation produces relatively long-lived (hundreds of nanoseconds to microsecond) MLCT excited states in high yields. These MLCT excited states, which are very strong reductants with E°(W+/*W0) = -2.2 to -3.0 V vs Fc[+/0], mediate photocatalysis of organic reactions with both visible and near-infrared (NIR) light. Here, we highlight design principles that led to the development of three generations of W(CNAr)6 photosensitizers; and we discuss likely steps in the mechanism of a prototypal W(CNAr)6-catalyzed base-promoted homolytic aromatic substitution reaction. Among the many potential applications of these very bright luminophores, two-photon imaging and two-photon-initiated polymerization are ones we plan to pursue.

A Systematic Review of Recruiting and Retaining Sociodemographically Diverse Families in Neurodevelopmental Research Studies.

Underrepresentation of socioeconomically, culturally, and/or linguistically diverse (SCLD) children with neurodevelopmental disorders (NDD) and their families has become a focal point for researchers. This systematic review aimed to identify researchers' strategies for recruiting and retaining SCLD families of children with NDD, published between 1993 and 2018. One hundred twenty-six articles were included, and study samples were categorized as "High SCLD" and "Low SCLD". Chi-square tests of independence were used to determine associations between sample composition (i.e., High/Low SCLD sample) and study characteristics reported. Significant associations were found between sample composition and studies that explicitly stated intention to recruit SCLD families, χ2(1) = 12.70, p < .001, Phi = 0.38 (moderate); and for studies that reported the following participant characteristics: language, χ2(1) = 29.58, p < .001, Phi = 0.48 (moderate-to-large); and race/ethnicity + SES + language, χ2(1) = 19.26, p <. 001, Phi = 0.39 (moderate). However, associations were not found between recruitment and retention approaches and whether studies included High SCLD or Low SCLD samples. Further study of NDD researchers' recruitment and retention approaches that successfully include SCLD families is needed.

Boronated Cyanometallates.

Thirteen boronated cyanometallates [M(CN-BR3)6]3/4/5- [M = Cr, Mn, Fe, Ru, Os; BR3 = BPh3, B(2,4,6,-F3C6H2)3, B(C6F5)3] and one metalloboratonitrile [Cr(NC-BPh3)6]3- have been characterized by X-ray crystallography and spectroscopy [UV-vis-near-IR, NMR, IR, spectroelectrochemistry, and magnetic circular dichroism (MCD)]; CASSCF+NEVPT2 methods were employed in calculations of electronic structures. For (t2g)5 electronic configurations, the lowest-energy ligand-to-metal charge-transfer (LMCT) absorptions and MCD C-terms in the spectra of boronated species have been assigned to transitions from cyanide π + B-C borane σ orbitals. CASSCF+NEVPT2 calculations including t1u and t2u orbitals reproduced t1u/t2u → t2g excitation energies. Many [M(CN-BR3)6]3/4- complexes exhibited highly electrochemically reversible redox couples. Notably, the reduction formal potentials of all five [M(CN-B(C6F5)3)6]3- anions scale with the LMCT energies, and Mn(I) and Cr(II) compounds, [K(18-crown-6)]5[Mn(CN-B(C6F5)3)6] and [K(18-crown-6)]4[Cr(CN-B(C6F5)3)6], are surprisingly stable. Continuous-wave and pulsed electron paramagnetic resonance (EPR; hyperfine sublevel correlation) spectra were collected for all Cr(III) complexes; as expected, 14N hyperfine splittings are greater for (Ph4As)3[Cr(NC-BPh3)6] than for (Ph4As)3[Cr(CN-BPh3)6].

A Qualitative Inquiry of Parents' Observations of Their Children's Mental Health Needs During the COVID-19 Pandemic.

Given that children and adolescents are at critical periods of development, they may be particularly vulnerable to the effects of the COVID-19 pandemic. Using a descriptive phenomenological approach, 71 parents' observations of their child's mental health difficulties were explored. Parents sought out treatment because their children were experiencing significant distress. Data used were transcribed from baseline questionnaires and therapy summaries. Data analysis revealed three themes: emotion regulation difficulties, hypervigilance, and despair. The search for strategies and tailored interventions to help mitigate the potential harmful and long-term mental health impacts of the pandemic should be at the forefront of research and clinical practice.

Photoredox Catalysis Mediated by Tungsten(0) Arylisocyanides in 1,2-Difluorobenzene.

We have studied the photochemical cyclization of 1-(2-iodobenzyl)-pyrrole (IBP) and 1-(2-bromobenzyl)-pyrrole (BBP) to 5H-pyrrolo[2,1-a]isoindol catalyzed by W(CNDipp)6 (CNDipp = 2,6-diisopropylphenylisocyanide) in 1,2-difluorobenzene (DFB). Irradiation (445 nm) of W(CNDipp)6 (5 mol %) in DFB solution converted 78% of IBP (50 mM) to product after 1 h (16 turnovers). Addition of tetra-n-butyl ammonium hexafluorophosphate (TBAPF6) (0.2 M) to the DFB solution led to rapid photoinduced disappearance of W(CNDipp)6 but, remarkably, did not inhibit photochemical cyclization of IBP, indicating that IBP cyclization could be driven by a nonluminescent photocatalyst.

Brief, parent-led, transdiagnostic cognitive-behavioral teletherapy for youth with emotional problems related to the COVID-19 pandemic.

BACKGROUND: The COVID-19 pandemic has led to increased stress, anxiety, and depression in children. A six-session, parent-led, transdiagnostic, cognitive-behavioral teletherapy program was adapted from an established protocol to help youth aged between 5 and 13 years manage emotional problems during the pandemic. METHODS: One-hundred twenty-nine parents of youth struggling with emotional problems during the COVID-19 pandemic participated in the program. Parents reported on their children's psychosocial functioning before and after treatment using validated assessments. They also reported on treatment satisfaction. Clinician-rated global improvement was assessed at each session to determine clinically significant treatment response. RESULTS: Significant improvements in parent proxy-reported anxiety (d = 0.56), depression (d = 0.69), stress (d = 0.61), anger (d = 0.69), family relationships (d = 0.32), and COVID-19-related distress (d = 1.08) were found, with 62% of participants who completed the program being classified as treatment responders. Parents reported high levels of satisfaction with the program. LIMITATIONS: This study was limited by use of primarily parent-report assessments and a lack of a control group. CONCLUSIONS: Brief, parent-led, transdiagnostic cognitive-behavioral teletherapy appeared to be an effective way to help youth cope with the pandemic and may be a scalable framework in response to large-scale mental health crises.

Photoredox Catalysis Mediated by Tungsten(0) Arylisocyanides.

W(CNAr)6 (CNAr = arylisocyanide) photoreductants catalyze base-promoted homolytic aromatic substitution (BHAS) of 1-(2-iodobenzyl)-pyrrole in deuterated benzene. Moderate to high efficiencies correlate with W(CNAr)6 excited-state reduction potentials upon one-photon 445 nm excitation, with 10 mol % loading of the most powerful photoreductants W(CNDipp)6 (CNDipp = 2,6-diisopropylphenylisocyanide) and W(CNDippPhOMe3)6 (CNDippPhOMe3 = 4-(3,4,5-trimethoxyphenyl)-2,6-diisopropylphenylisocyanide) affording nearly complete conversion. Stern-Volmer quenching experiments indicated that catalysis is triggered by substrate reductive dehalogenation. Taking advantage of the large two-photon absorption (TPA) cross sections of W(CNAr)6 complexes, we found that photocatalysis can be driven with femtosecond-pulsed 810 nm excitation. For both one- and two-photon excitation, photocatalysis was terminated by the formation of seven-coordinate WII-diiodo [WI2(CNAr)5] complexes. Notably, we discovered that W(CNDipp)6 can be regenerated by chemical reduction of WI2(CNDipp)5 with excess ligand present in solution.

Electronic Structures, Spectroscopy, and Electrochemistry of [M(diimine)(CN-BR3)4]2- (M = Fe, Ru; R = Ph, C6F5) Complexes.

Complexes with the formula [M(diimine)(CN-BR3)4]2-, where diimine = bipyridine (bpy), phenanthroline (phen), 3,5-trifluoromethylbipyridine (flpy), R = Ph, C6F5, and M = FeII, RuII, were synthesized and characterized by X-ray crystal structure analysis, UV-visible spectroscopy, IR spectroscopy, and voltammetry. Three highly soluble complexes, [FeII(bpy)(CN-B(C6F5)3)4]2-, [RuII(bpy)(CN-B(C6F5)3)4]2-, and [RuII(flpy)(CN-B(C6F5)3)4]2-, exhibit electrochemically reversible redox reactions, with large potential differences between the bpy0/- or flpy0/- and MIII/II couples of 3.27, 3.52, and 3.19 V, respectively. CASSCF+NEVPT2 calculations accurately reproduce the effects of borane coordination on the electronic structures and spectra of cyanometallates.

Spin-phonon coupling and dynamic zero-field splitting contributions to spin conversion processes in iron(II) complexes.

Magnetization dynamics of transition metal complexes manifest in properties and phenomena of fundamental and applied interest [e.g., slow magnetic relaxation in single molecule magnets, quantum coherence in quantum bits (qubits), and intersystem crossing (ISC) rates in photophysics]. While spin-phonon coupling is recognized as an important determinant of these dynamics, additional fundamental studies are required to unravel the nature of the coupling and, thus, leverage it in molecular engineering approaches. To this end, we describe here a combined ligand field theory and multireference ab initio model to define spin-phonon coupling terms in S = 2 transition metal complexes and demonstrate how couplings originate from both the static and dynamic properties of ground and excited states. By extending concepts to spin conversion processes, ligand field dynamics manifest in the evolution of the excited state origins of zero-field splitting (ZFS) along specific normal mode potential energy surfaces. Dynamic ZFSs provide a powerful means to independently evaluate contributions from spin-allowed and/or spin-forbidden excited states to spin-phonon coupling terms. Furthermore, ratios between various intramolecular coupling terms for a given mode drive spin conversion processes in transition metal complexes and can be used to analyze the mechanisms of ISC. Variations in geometric structure strongly influence the relative intramolecular linear spin-phonon coupling terms and will define the overall spin state dynamics. While the findings of this study are of general importance for understanding magnetization dynamics, they also link the phenomenon of spin-phonon coupling across fields of single molecule magnetism, quantum materials/qubits, and transition metal photophysics.