Rare Spin Research Articles

Chirality Versus Symmetry: Electron's Spin Selectivity in Nonpolar Chiral Lead-Bromide Perovskites.

In the last decade, chirality-induced spin selectivity (CISS), the spin-selective electron transport through chiral molecules, has been described in a large range of materials, from insulators to superconductors. Because more experimental studies are desired for the theoretical understanding of the CISS effect, chiral metal-halide semiconductors may contribute to the field thanks to their chiroptical and spintronic properties. In this regard, this work uses new chiral organic cations S-HP1A and R-HP1A (HP1A = 2-hydroxy-propyl-1-ammonium) to prepare 2D chiral halide perovskites (HPs) which crystallize in the enantiomorphic space groups P43 21 2 and P41 21 2, respectively. The fourfold symmetry induces antiferroelectricity along the stacking axis which, combined to incomplete Rashba-like splitting in each individual 2D polar layer, results in rare spin textures in the band structure. As revealed by magnetic conductive-probe atomic force microscopy (AFM) measurements, these materials show CISS effect with partial spin polarization (SP; ±40-45%). This incomplete effect is efficient enough to drive a chiro-spintronic device as demonstrated by the fabrication of spin valve devices with magnetoresistance (MR) responses up to 250 K. Therefore, these stable lead-bromide HP materials not only represent interesting candidates for spintronic applications but also reveal the importance of polar symmetry-breaking topology for spin selectivity.

Efficient Spin-Orbit Charge-Transfer Intersystem Crossing and Slow Intramolecular Triplet-Triplet Energy Transfer in Bodipy-Perylenebisimide Compact Dyads and Triads.

Bodipy (BDP)-perylenebisimide (PBI) donor-acceptor dyads/triad were prepared to study the spin-orbit charge-transfer intersystem crossing (SOCT-ISC). For BDP-PBI-3, in which BDP was attached at the imide position of PBI, higher singlet oxygen quantum yield (ΦΔ =85 %) was observed than the bay-substituted derivative BDP-PBI-1 (ΦΔ =30 %). Femtosecond transient absorption spectra indicate slow Förster resonance energy transfer (FRET; 40.4 ps) and charge separation (CS; 1.55 ns) in BDP-PBI-3, while for BDP-PBI-1, CS takes 2.8 ps. For triad BDP-PBI-2, ultrafast FRET (149 fs) and CS (4.7 ps) process were observed, the subsequent charge recombination (CR) takes 5.8 ns and long-lived 3 PBI* (179.8 μs) state is populated. Nanosecond transient absorption spectra of BDP-PBI-3 show that the CR gives upper triplet excited state (3 BDP*) and subsequently, via a slow intramolecular triplet energy transfer (14.5 μs), the 3 PBI* state is finally populated, indicating that upper triplet state is involved in SOCT-ISC. Time-resolved electron paramagnetic resonance spectroscopy revealed that both radical pair ISC (RP ISC) and SOCT-ISC contribute to the ISC. A rare electron spin polarization of (e, e, e, e, e, e) was observed for the triplet state formed via the RP ISC mechanism, due to the S-T+1 /T0 states mixing.

Rare Spin Avoided σ-σ Diradical Planar Tetracoordinate Boron Cluster: A Proto-Star for Planar Pentacoordination.

We report a global planar star-like cluster B3Li3 featuring three planar tetracoordinate boron centres with a rare spin avoided σ-σ diradical character. The cluster was found to be stable towards dissociation into different fragments. The spin density was found to be localized solely on the three boron atoms in the molecular plane. This spin avoided σ-σ diradical character leads to the extension of the coordination number to yield a neutral B3Li3H3 and a cationic B3Li3H3+ cluster with three planar pentacoordinate boron centres in their global minimum structures. The planar geometry of the aninonic B3Li3H3- cluster is slightly higher in energy. The planar global clusters were found to maintain planarity in their ligand protected benzene bound complexes, B3Li3(Bz)3, B3Li3H3(Bz)3 and B3Li3H3(Bz)3+ with high ligand dissociation energies offering candidature for experimental detection.

Futuristic storage devices: Single molecular magnets of rare earths versus spin crossover systems of earth-abundant metals

Futuristic storage devices: Single molecular magnets of rare earths versus spin crossover systems of earth-abundant metals

Vibronic Relaxation Pathways in Molecular Spin Qubit Na9[Ho(W5O18)2]·35H2O under Pressure

In order to explore how spectral sparsity and vibronic decoherence pathways can be controlled in a model qubit system with atomic clock transitions, we combined diamond anvil cell techniques with synchrotron-based far infrared spectroscopy and first-principles calculations to reveal the vibrational response of Na9[Ho(W5O18)2]·35H2O under compression. Because the hole in the phonon density of states acts to reduce the overlap between the phonons and f manifold excitations in this system, we postulated that pressure might move the HoO4 rocking, bending, and asymmetric stretching modes that couple with the MJ = ±5, ±2, and ±7 levels out of resonance, reducing their interactions and minimizing decoherence processes, while a potentially beneficial strategy for some molecular qubits, pressure slightly hardens the phonons in Na9[Ho(W5O18)2]·35H2O and systematically fills in the transparency window in the phonon response. The net result is that the vibrational spectrum becomes less sparse and the overlap with the various MJ levels of the Ho3+ ion actually increases. These findings suggest that negative pressure, achieved using chemical means or elongational strain, could further open the transparency window in this rare earth-containing spin qubit system, thus paving the way for the use of device surfaces and interface elongational/compressive strains to better manage decoherence pathways.

Nuclear dipolar relaxation induced by interacting ground state electron spins

In samples used for dynamic nuclear polarization (DNP), spin–lattice relaxation times are usefully increased by going to high magnetic field and low temperature, typically several tesla and below 1 K. But the relaxation times for dipolar components of the nuclear spin energy remain stubbornly shorter than those for the Zeeman energy: dipolar order decays faster than the polarization itself by a huge factor—up to four orders of magnitude or more in the materials studied thus far. Such fast nuclear dipolar relaxation poses experimental challenges, for instance, when transferring polarization between different nuclear spin species via intermediate nuclear order: a proven technique to polarize rare nuclear spins. The origin of this fast nuclear dipolar relaxation remained a mystery for a long time—existing theories of nuclear spin–lattice relaxation could at best predict about one order of magnitude difference between the nuclear dipolar and nuclear Zeeman relaxation rates—until it was recently discovered to be due to conversion of nuclear dipolar energy into super-hyperfine energy induced by nuclear flip-flop transitions. A previous article showed that the inclusion of this relaxation path enables a quantitative explanation of nuclear dipolar relaxation induced by photo-excited triplet states. This article extends the theory to nuclear dipolar relaxation induced by ground state electron spins and demonstrates that this new mechanism enables a precise quantitative prediction from first principles of the nuclear dipolar relaxation rate for Ca(OH)2 doped with O2- centres—in which DNP is caused by the solid effect (SE)—and LiF doped with F-centres—in which DNP is caused by thermal mixing (TM)—both at 5.5 T and 0.4 K. It is noticed that the proposed mechanism extends to other spin systems which has implications for e.g. TM and spectral diffusion.

Prompt acceleration of a μ + beam in a toroidal wakefield driven by a shaped steep-rising-front Laguerre–Gaussian laser pulse

Recent experimental data for anomalous magnetic moments strongly indicates the existence of new physics beyond the Standard Model. Energetic μ + bunches are relevant to μ + rare decay, spin rotation, resonance and relaxation (μSR) technology, future muon colliders, and neutrino factories. In this paper, we propose prompt μ + acceleration in a nonlinear toroidal wakefield driven by a shaped steep-rising-front Laguerre–Gaussian (LG) laser pulse. An analytical model is described, which shows that a μ + beam can be focused by an electron cylinder at the centerline of a toroidal bubble and accelerated by the front part of the longitudinal wakefield. A shaped LG laser with a short rise time can push plasma electrons, generating a higher-density electron sheath at the front of the bubble, which can enhance the acceleration field. The acceleration field driven by the shaped steep-rising-front LG laser pulse is about four times greater than that driven by a normal LG laser pulse. Our simulation results show that a 300 MeV μ + bunch can be accelerated to 2 GeV and its transverse size is focused from an initial value of w 0 = 5 μm to w = 2 μm in the toroidal bubble driven by the shaped steep-rising-front LG laser pulse with a normalized amplitude of a = 22.

Some aspects of transition selective NMR involving rare spins

Satellite transition selective excitation/inversion of abundant spins across chemical shifts offers a robust opportunity for sensitivity enhancement of rare spins that are coupled to them. It is also well established that reconversion of rare spin double quantum coherence (DQC) to single quantum-single transitions (SQ-ST's) over a wide range of chemical shifts offers sensitivity enhancement in INADEQUATE-style experiments. The present contribution gives an overview of the latter category of experiments, including a brief summary of the literature, and the contributions from our Lab. In particular, the transition selective “composite refocusing” approach of Sørensen and his group is discussed for reconversion of DQC to SQ-ST's. A shorter transition selective DQC reconversion module introduced from our Lab is also described. A 2D rare spin correlation experiment introduced by us is then reviewed, in which we replace rare spin DQ evolution with immediate reconversion of DQC to SQ-ST's, followed by evolution of SQ-ST's, that is then terminated by a mixing period to deliver a diagonal-free COSY-like correlation map. Finally, our ‘indirect’, 1H detected version of this experiment is reviewed. Transition selective reconversion in ADEQUATE-style experiments was also introduced by us and is briefly mentioned. Interestingly, partial 1H transition selectivity is shown to result as a consequence of reconversion of rare spin DQC to SQ-ST's, followed by coherence order selective heteronuclear reverse transfer. The performance of these experiments when applied to small molecules is illustrated.

Extreme-value statistics of the spin of primordial black holes

How rare are extreme-spin primordial black holes? We show how, from an underlying distribution of primordial black hole (PBH) spin, extreme-value statistics can be used to quantify the rarity of spinning PBHs with Kerr parameter close to 1. Using the peaks-over-threshold method, we show how the probability that a PBH forms with spin exceeding a sufficiently high threshold can be calculated using the generalized Pareto distribution. This allows us to estimate the average number of PBHs amongst which we can find a single PBH that formed with spin exceeding a high threshold. We found that the primordial spin distribution gives rise to exceedingly rare near-extremal spin PBHs at formation time: for typical parameter values, roughly up to one in a hundred million PBHs would be formed with spin exceeding the Thorne limit. We discuss conditions under which even more extreme-spin PBHs may be produced, including modifying the skewness and kurtosis of the spin distribution via a smooth transformation. We deduce from our calculations that, if indeed asteroid-mass PBHs above the current observational limit on evaporating PBHs of mass $\ensuremath{\sim}{10}^{17}\text{ }\text{ }\mathrm{g}$ contribute significantly to the dark matter, it is very likely that some of them at somewhat lower masses could be long-lived near-extremal PBHs.

Enhancement of spin Seebeck effect of reverse spin crossover Fe (II) micellar charge transport using PMMA polymer electrolyte

The electrochemical thermoelectric effect is capable of generating Seebeck and conductivity from a temperature gradient through redox reaction at the electrode. Conventional spin Seebeck effect (SSE) is the generation of spin voltage by solid coupling magnetic thin film in presence of magnetic field and temperature gradient. In this study, we demonstrate an enhancement of a magnetic free SSE of Fe (II) reverse spin‐crossover in electrolyte using 1% PMMA polymer additive in form of polymer electrolyte. The reverse spin effect of Fe (II) complex, which is confirmed by SQUID magnetometer analysis and DFT simulation, is able to produce magnetic free SSE in solution. A unique electrochemical behavior is found in form of SSE Fe (II) polymer electrolyte that is elucidated using cyclic voltammetry, electrochemical impedance spectroscopy, and UV‐Vis analysis. The polymer electrolyte that possesses strong spin Seebeck produces a maximum Seebeck coefficient and conductivity of 124 % and 233 % higher than that weak SSE and conventional liquid electrolyte. The spin Seebeck produces a high number of carrier density through fast diffusion at high spin state, and the opposite charge properties trend at low spin state. Cryo‐TEM analysis had shown that the generation of spin Seeebeck effect of the Fe (II) complex in solution also involves reverse spherical micelles formation. Thus, this study highlights the finding of a rare magnetic free spin Seebeck generation in polymer electrolyte that having potential for waste heat recycles, heat sensors, and thermal switches applications upon development.

Decoherence optimized tilted-angle cross polarization: A novel concept for sensitivity-enhanced solid-state NMR using ultra-fast magic angle spinning

Ultra-fast magic-angle spinning (UFMAS) at a MAS rate (ωR/2π) of 60 kHz or higher has dramatically improved the resolution and sensitivity of solid-state NMR (SSNMR). However, limited polarization transfer efficiency using cross-polarization (CP) between 1H and rare spins such as 13C still restricts the sensitivity and multi-dimensional applications of SSNMR using UFMAS. We propose a novel approach, which we call decoherence-optimized tilted-angle CP (DOTA CP), to improve CP efficiency with prolonged lifetime of 1H coherence in the spin-locked condition and efficient band-selective polarization transfer by incorporating off-resonance irradiation to 1H spins. 13C CP-MAS at ωR/2π of 70–90 kHz suggested that DOTA CP notably outperformed traditional adiabatic CP, a de-facto-standard CP scheme over the past decade, in sensitivity for the aliphatic-region spectra of 13C-labeled GB1 protein and N-formyl-Met-Leu-Phe samples by up to 1.4- and 1.2-fold, respectively. 1H-detected 2D 1H/13C SSNMR for the GB1 sample indicated the effectiveness of this approach in various multidimensional applications.

Interesting spin state properties of iron(II) polypyridine complex substituted by fluorine: A theoretical study

The special iron(II) polypyridyl complex substituted by fluorine ([Fe(dftpy)2]2+, dftpy = 6,6″-difluoro-2,2’; 6′2″-terpyridine) with uncommon mixed ground states has been detected recently, but the related explanation and characterization are not enough, especially for the influence of substituents. On the basis of previous studies, the key problem of mixed spin states is expected to be described very well by means of theoretical calculations. In this work, density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations have been carried out to study the characteristics of the excited states in detail. Comparing with the parent complex [Fe(tpy)2]2+ (tpy = 2,2′:6′,2″-terpyridine) and corresponding bromine or chlorine substituted derivates, the ground states of [Fe(dftpy)2]2+ stay around the mixture of singlet state and quintet state, but also there is rare high spin excited state lifetime. Among the halogen substituted complexes, [Fe(dftpy)2]2+ has the shortest MLCT state lifetime of 14.0 ps which has been much longer than subpicosecond lifetime of [Fe(tpy)2]2+. The reason is explored by the combination of electronic structures, absorption properties, extended transition state coupled with natural orbitals for chemical valence (ETS-NOCV) and potential energy curves (PECs). We can find that the bond lengths of Fe-Nt play a significant role on the change of metal centered (MC) ground states. With Fe-Nt extended by fluorine atoms, the quintet state becomes lower than the singlet state. Due to the deformation of structures, the interactions between metal and ligands diminish and give rise to weaker d orbital splitting than that of [Fe(tpy)2]2+, but slightly impact the pairwise orbital deformation density characteristics. And the PEC of 5MC intersects with 1,3MC which renders faster non-radiative deactivation through low-lying energy crossing points.

Can proton-proton recoupling in fully protonated solids provide quantitative, selective and efficient polarization transfer?

Dipolar recoupling sequences have been used to probe spatial proximity of nuclear spins and were traditionally designed to probe rare spins such as 13C and/or 15N nuclei. The multi-spin dipolar-coupling network of the rare spins is weak due to smaller couplings and large chemical shift dispersion. Therefore, the recoupling approaches were tailored to design offset compensated or broadband sequences. In contrast, protons have a substantially stronger dipolar-coupling network and much narrower chemical shift range. Broadband recoupling sequences such as radio-frequency driven recoupling (RFDR), back-to-back (BABA), and lab frame proton-proton spin diffusion have been routinely used to characterize the structures of protein/macromolecules and small molecules. Recently selective 1H-1H recoupling sequences have been proposed that combine chemical shift offset of the resolved proton spectrum (at fast MAS) with first- and second-order dipolar recoupling Hamiltonians to obtain quantitative and qualitative proton distances, respectively. Herein, we evaluate the performances of broadband and selective proton recoupling sequences such as finite pulse RFDR (fp-RFDR), band-selective spectral spin diffusion (BASS-SD), second-order cross-polarization (SOCP), and selective recoupling of proton (SERP) in terms of the selectivity and efficiency of 1H-1H polarization transfers in a dense network of proton spins and explore the possibility of measuring 1H-1H distances. We use theoretical considerations, numerical simulations, and experiments to support the distinct advantages and disadvantages of each recoupling sequence. Experiments were performed on L-histidine.HCl.H2O at a MAS frequency of 71.43 kHz. This study rationalizes the proper selection of 1H-1H recoupling sequences when working with fully protonated solids.

Multimodal Structure Solution with 19F NMR Crystallography of Spin Singlet Molybdenum Oxyfluorides.

Complex crystal structures with subtle atomic-scale details are now routinely solved using complementary tools such as X-ray and/or neutron scattering combined with electron diffraction and imaging. Identifying unambiguous atomic models for oxyfluorides, needed for materials design and structure-property control, is often still a considerable challenge despite their advantageous optical responses and applications in energy storage systems. In this work, NMR crystallography and single-crystal X-ray diffraction are combined for the complete structure solution of three new compounds featuring a rare triangular early transition metal oxyfluoride cluster, [Mo3O4F9]5-. After framework identification by single-crystal X-ray diffraction, 1D and 2D solid-state 19F NMR spectroscopy supported by ab initio calculations are used to solve the structures of K5[Mo3O4F9]·3H2O (1), K5[Mo3O4F9]·2H2O (2), and K16[Mo3O4F9]2[TiF6]3·2H2O (3) and to assign the nine distinct fluorine sites in the oxyfluoride clusters. Furthermore, 19F NMR identifies selective fluorine dynamics in K16[Mo3O4F9]2[TiF6]3·2H2O. These dual scattering and spectroscopy methods are used to demonstrate the generality and sensitivity of 19F shielding to small changes in bond length, on the order of 0.01 Å or less, even in the presence of hydrogen bonding, metal-metal bonding, and electrostatic interactions. Starting from the structure models, the nature of chemical bonding in the molybdates is explained by molecular orbital theory and electronic structure calculations. The average Mo-Mo distance of 2.505 Å and diamagnetism in 1, 2, and 3 are attributed to a metal-metal bond order of unity along with a 1a21e4 electronic ground state configuration for the [Mo3O4F9]5- cluster, leading to a rare trimeric spin singlet involving d2 Mo4+ ions. The approach to structure solution and bonding analysis is a powerful strategy for understanding the structures and chemical properties of complex fluorides and oxyfluorides.

SABRE polarized low field rare-spin spectroscopy.

High-field nuclear magnetic resonance (NMR) spectroscopy is an indispensable technique for identification and characterization of chemicals and biomolecular structures. In the vast majority of NMR experiments, nuclear spin polarization arises from thermalization in multi-Tesla magnetic fields produced by superconducting magnets. In contrast, NMR instruments operating at low magnetic fields are emerging as a compact, inexpensive, and highly accessible alternative but suffer from low thermal polarization at a low field strength and consequently a low signal. However, certain hyperpolarization techniques create high polarization levels on target molecules independent of magnetic fields, giving low-field NMR a significant sensitivity boost. In this study, SABRE (Signal Amplification By Reversible Exchange) was combined with high homogeneity electromagnets operating at mT fields, enabling high resolution 1H, 13C, 15N, and 19F spectra to be detected with a single scan at magnetic fields between 1 mT and 10 mT. Chemical specificity is attained at mT magnetic fields with complex, highly resolved spectra. Most spectra are in the strong coupling regime where J-couplings are on the order of chemical shift differences. The spectra and the hyperpolarization spin dynamics are simulated with SPINACH. The simulations start from the parahydrogen singlet in the bound complex and include both chemical exchange and spin evolution at these mT fields. The simulations qualitatively match the experimental spectra and are used to identify the spin order terms formed during mT SABRE. The combination of low field NMR instruments with SABRE polarization results in sensitive measurements, even for rare spins with low gyromagnetic ratios at low magnetic fields.

Robustness in Coupling between Iron and Rare Earth Spins in Rare Earth Orthoferrites

We report on very accurate magnetic measurements on large rare earth orthoferrites single crystals of ErFeO3 and NdFeO3. Our results show that the interaction between rare earth and iron spin system does not change during the spin-flip process. This implies that the coupling between the iron and rare earth spin systems is robust enough to withstand the effects of spin flipping against the magnetic anisotropy energy. This is despite rare eath ions, polarized by the ordered iron ions, being in partly metastable state and their magnetic moment decays with time.

Magnetic Interaction between Pr3+ and Dy3+ Spins and Their Spin Transition Induced by Magnetic Field in a Dy0.5Pr0.5FeO3 Single Crystal

Rare earth orthoferrites are receiving ever-increasing attention for their potential applications in magneto-optical switching, multiferroics and novel physics originating from complicated interactions between magnetic rare earth and iron ions. In this work, Dy0.5Pr0.5FeO3 single crystal was studied in comparison with DyFeO3 and PrFeO3 single crystals, to ascertain effects of interactions between rare earth spins in Dy0.5Pr0.5FeO3 on its magnetic properties. Dy3+ and Pr3+ spins do not behave as separate entities in Dy0.5Pr0.5FeO3. The interaction between them was found to be the strongest below their antiferromagnetic ordering temperature. However, this interaction still persists to substantially higher temperatures. While the ordering temperature of Dy3+ spins is field-independent for DyFeO3, it becomes strongly field-dependent for Dy0.5Pr0.5FeO3. External field produces field-polarization of non-ordered rare earth spins below ~25 K for all three systems. High-field-induced spin transition of rare earth ...

Iron(III) Azadiphenolate Compounds in a New Family of Spin Crossover Iron(II)–Iron(III) Mixed-Valent Complexes

A new family of mixed valent, double salt spin crossover compounds containing anionic FeIII and cationic FeII compounds i.e., [FeII{(pz)3CH}2][FeIII(azp)2]2·2H2O (4), [FeII(TPPZ)2][FeIII(azp)2]2]·H2O (5) and [FeII(TPPZ)2][FeIII(azp)2]2]·H2O·3MeCN (6) (where (pz)3CH = tris-pyrazolylmethane, TPPZ = 2,3,5,6, tetrapyridylpyrazine and azp2− = azadiphenolato) has been synthesized and characterised. This is the first time that the rare anionic spin crossover species, [FeIII(azp)2]−, has been used as an anionic component in double salts complexes. Single crystal structures and magnetic studies showed that compound 6 exhibits a spin transition relating to one of the FeIII centres of the constituent FeII and FeIII sites. Crystal structures of the anionic and cationic precursor complexes were also analysed and compared to the double salt products thus providing a clearer picture for future crystal design in double spin crossover materials. We discuss the effects that the solvent and counterion had on the crystal packing and spin crossover properties.

High-Cooperativity Coupling of a Rare-Earth Spin Ensemble to a Superconducting Resonator Using Yttrium Orthosilicate as a Substrate

Yttrium orthosilicate (Y$_2$SiO$_5$, or YSO) has proved to be a convenient host for rare-earth ions used in demonstrations of microwave quantum memories and optical memories with microwave interfaces, and shows promise for coherent microwave--optical conversion owing to its favourable optical and spin properties. The strong coupling required by such microwave applications could be achieved using superconducting resonators patterned directly on Y$_2$SiO$_5$, and hence we investigate here the use of Y$_2$SiO$_5$ as an alternative to sapphire or silicon substrates for superconducting hybrid device fabrication. A NbN resonator with frequency 6.008 GHz and low power quality factor $Q \approx 400000$ was fabricated on a Y$_2$SiO$_5$ substrate doped with isotopically enriched Nd$^{145}$. Measurements of dielectric loss yield a loss-tangent $\tan\delta = 4 \times 10^{-6}$, comparable to sapphire. Electron spin resonance (ESR) measurements performed using the resonator show the characteristic angular dependence expected from the anisotropic Nd$^{145}$ spin, and the coupling strength between resonator and electron spins is in the high cooperativity regime ($C = 30$). These results demonstrate Y$_2$SiO$_5$ as an excellent substrate for low-loss, high-Q microwave resonators, especially in applications for coupling to optically-accessible rare earth spins.

Theoretical study on the excited state decay properties of iron(ii) polypyridine complexes substituted by bromine and chlorine.

Transition metal iron(ii) polypyridyl complexes with quintet ground states were deeply investigated by density functional theory (DFT) and time-dependent density functional theory (TDDFT). Compared with the parent complex [Fe(tpy)2]2+ (tpy = 2,2′:6′,2′′-terpyridine), the ground states of the complexes substituted by halogen atoms changed from singlet states to quintet states with rare high spin excited state lifetimes. The substituted complex [Fe(dbtpy)2]2+ (1) results in a high spin metal–ligand charge transfer lifetime of 17.4 ps, which is 1.4 ps longer than that of [Fe(dctpy)2]2+ (2) with the substitution of chlorine atoms. The reason for this is explored by a combination of electronic structures, absorption spectra, extended transition state coupled with natural orbitals for chemical valence (ETS-NOCV) studies and potential energy curves (PECs). The distortion of 1 in the angles and dihedrals of the ligands is slightly larger than that in 2, although the average metal–ligand bond lengths of the latter are larger. The twisted octahedron decreases the interactions between the d orbitals of iron(ii) and the n/π orbitals of the ligands. Compared with 2, the enlarged energy gaps among the different PECs of 1 and the increased energy crossing points caused by the larger distortion result in the increase of its excited state lifetime. The different pairwise orbital interaction contributions between the metal center and the ligands in their singlet states are qualitatively estimated by ETS-NOCV. The results show that the substitution of bromine atoms will decrease the electrostatic attraction between the metal and ligands but not significantly impact the orbital interactions.