Homoleptic Cyclic Trinuclear d10 Complexes: From Self-Association via Metallophilic and Excimeric Bonding to the Breakage Thereof via Oxidative Addition, Dative Bonding, Quadrupolar and Heterometal Bonding Interactions

Trinuclear coinage metal metallacycles are obtained when two-coordinate metals are bonded to C, N or N, N anionic ligands of the proper symmetry to form cycles where metals alternate with bridging ligands. Cyclotrimers often exhibit semiplanar structures and mostly columnar or finite stacking in the solid state by means of metallophilic interactions. They show some peculiar properties with an impact on many different fields such as supramolecular architectures, luminescence, molecular recognition, host-guest chemistry, and acid-base chemistry. The comprehensive evaluation of the data shows that, depending on the nature of the central metal and bridging ligand, there is a fine balance of the energy involved in the inter-trimer bond cleavages and the energy gained from the formation of new intermolecular electrostatic interactions, proceeding occasionally to the chemical extreme of redox processes. In this review, a number of important developments are highlighted and systematically analyzed along with structural and computational data and chemical properties to rationalize and build a unifying leitmotif for this chemistry; the focus is made on the authors’ contributions in these areas

Impact of opioid-free analgesia on pain severity and patient satisfaction after discharge from surgery: multispecialty, prospective cohort study in 25 countries

Background: Balancing opioid stewardship and the need for adequate analgesia following discharge after surgery is challenging. This study aimed to compare the outcomes for patients discharged with opioid versus opioid-free analgesia after common surgical procedures.Methods: This international, multicentre, prospective cohort study collected data from patients undergoing common acute and elective general surgical, urological, gynaecological, and orthopaedic procedures. The primary outcomes were patient-reported time in severe pain measured on a numerical analogue scale from 0 to 100% and patient-reported satisfaction with pain relief during the first week following discharge. Data were collected by in-hospital chart review and patient telephone interview 1 week after discharge.Results: The study recruited 4273 patients from 144 centres in 25 countries; 1311 patients (30.7%) were prescribed opioid analgesia at discharge. Patients reported being in severe pain for 10 (i.q.r. 1-30)% of the first week after discharge and rated satisfaction with analgesia as 90 (i.q.r. 80-100) of 100. After adjustment for confounders, opioid analgesia on discharge was independently associated with increased pain severity (risk ratio 1.52, 95% c.i. 1.31 to 1.76; P < 0.001) and re-presentation to healthcare providers owing to side-effects of medication (OR 2.38, 95% c.i. 1.36 to 4.17; P = 0.004), but not with satisfaction with analgesia (beta coefficient 0.92, 95% c.i. -1.52 to 3.36; P = 0.468) compared with opioid-free analgesia. Although opioid prescribing varied greatly between high-income and low- and middle-income countries, patient-reported outcomes did not.Conclusion: Opioid analgesia prescription on surgical discharge is associated with a higher risk of re-presentation owing to side-effects of medication and increased patient-reported pain, but not with changes in patient-reported satisfaction. Opioid-free discharge analgesia should be adopted routinely

Electronic Structure Studies of Six-Atom Gold Clusters

Electronic structures of hexagold phosphine-stabilized complex and related systems were calculated using density functional theory (DFT), Hartree-Fock (HF) and configuration interaction (CI) methods. The absorption spectra of gold clusters were simulated using the CI wave functions and energies. A larger energy was required for the removal of two electrons from a bare gold cluster as compared to a cluster with phosphine ligands