Three structurally diverse 5-phenyl­tetra­zolato (Tz) Ti, Zr, and Ta com­plexes, namely, (C2H8N)[Ti2(C7H5N4)5(C2H6N)4]·1.45C6H6 or (Me2NH2)[Ti2(NMe2)4(2,3-μ-Tz)3(2-η1-Tz)2]·1.45C6H6, (1·1.45C6H6), [Zr2(C7H5N4)6(C2H6N)2(C2H7N)2]·1.12C6H6·0.382CH2Cl2 or [Zr2(Me2NH)2(NMe2)2(2,3-μ-Tz)3(2-η1-Tz)2(1,2-η2-Tz)]·1.12C6H6·0.38CH2Cl2 (2·1.12C6H6·0.38CH2Cl2), and (C2H8N)2[Ta2(C7H5N4)8(C2H6N)2O]·0.25C7H8 or (Me2NH2)2[Ta2(NMe2)2(2,3-μ-Tz)2(2-η1-Tz)6O]·0.25C7H8 (3·0.25C7H8), where TzH is 5-phenyl-1H-tetra­zole, have been synthesized and structurally characterized. All three com­plexes are dinuclear; the Ti center in 1 is six-coordinate, whereas the Zr and Ta atoms in 2 and 3 are seven-coordinate. The coordination environments of the Ti centers in 1 are similar, and so are the ligations of the Ta centers in 3. In contrast, the two Zr centers in 2 bear a different number of ligands, one of which is a bidentate η2-5-phenyl­tetra­zolato ligand that has not been observed previously for d-block elements. The di­methyl­amido ligand, present in the starting materials, remained un­changed, or was converted to di­methyl­amine and di­methyl­ammonium during the synthesis. Di­methyl­amine coordinates as a neutral ligand, whereas di­methyl­ammonium is retained as a hy­dro­gen-bonded entity bridging Tz ligands.

The crystal structures of two coordination com­pounds, (acetato-κO)(2,2'-bi­py­ri­dine-κ2N,N')(1,10-phenanthroline-κ2N,N')copper(II) acetate hexa­hydrate, [Cu(C2H3O2)(C10H8N2)(C12H8N2)](C2H3O2)·6H2O or [Cu(bipy)(phen)Ac]Ac·6H2O, and (acetato-κO)bis­(2,2'-bi­py­ri­dine-κ2N,N')copper(II) acetate–acetic acid–water (1/1/3), [Cu(C2H3O2)(C10H8N2)2](C2H3O2)·C2H4O2·3H2O or [Cu(bipy)2Ac]Ac·HAc·3H2O, are reported and com­pared with the previously published structure of [Cu(phen)2Ac]Ac·7H2O (phen is 1,10-phenanthroline, bipy for 2,2'-bi­py­ri­dine, ac is acetate and Hac is acetic acid). The geometry around the metal centre is penta­coordinated, but highly distorted in all three cases. The coordination number and the geometric distortion are both discussed in detail, and all com­plexes belong to the space group Poverline{1}. The analysis of the geometric parameters and the Hirshfeld surface properties dnorm and curvedness provide information about the metal–ligand inter­actions in these com­plexes and allow com­parison with similar systems.

The synthesis and structural characterization of four novel supra­molecular hy­dro­gen-bonded arrangements based on self-assembly from mol­ecular `[Cu(2,2'-bi­imid­az­ole)]' modules and malonate anions are pre­sent­ed, namely, tetra­kis­(2,2'-bi­imid­az­ole)di-μ-chlorido-dimal­on­atotricopper(II) penta­hydrate, [Cu3(C3H2O4)2Cl2(C6H6N4)4]·5H2O or [Cu(H2biim)2(μ-Cl)Cu0.5(mal)]2·5H2O, aqua­(2,2'-bi­imid­az­ole)­mal­on­atocopper(II) dihydrate, [Cu(C3H2O4)(C6H6N4)(H2O)]·2H2O or [Cu(H2biim)(mal)(H2O)]·2H2O, bis­[aqua­bis­(2,2'-bi­imid­az­ole)­cop­per(II)] di­mal­on­atodi­perchloratocopper(II) 2.2-hydrate, [Cu(C6H6N4)2(H2O)]2[Cu(C3H2O4)(ClO4)2]·2.2H2O or [Cu(H2biim)2(H2O)]2[Cu(mal)2(ClO4)2]·2.2H2O, and bis­(2,2'-bi­imid­az­ole)­copper(II) bis­[bis­(2,2'-bi­imid­az­ole)(2-carb­oxy­acetato)mal­on­atocopper(II)] tridecahydrate, [Cu(C6H6N4)2][Cu(C3H2O4)(C3H3O4)(C6H6N4)2]·13H2O or [Cu(H2biim)2][Cu(H2biim)2(Hmal)(mal)]2·13H2O. These as­sem­blies are characterized by self-com­plementary donor–acceptor mol­ecular inter­actions, demonstrating a recurrent and distinctive pattern of hy­dro­gen-bonding preferences among the carboxyl­ate, carb­oxy­lic acid and N—H groups of the coordinated 2,2'-bi­imid­az­ole and malonate ligands. Additionally, co­or­din­ation of the carboxyl­ate group with the metallic centre helps sustain re­mark­able supra­molecular assemblies, such as layers, helices, double helix columns or 3D channeled architectures, including mixed-metal com­plexes, into a single structure.

In the title compound, (2-methyl­idene-1,2-di­hydro­pyridinium-κN)tris­(tetra­hydro­furan-κO)lithium, [Li(C6H6N)(C4H8O)3], the lithium ion adopts a distorted LiNO3 tetra­hedral coordination geometry and the 2-picolyl anion adopts its enamido form with the lithium ion lying close to the plane of the pyridine ring. A methyl­ene group of one of the thf ligands is disordered over two orientations. In the crystal, a weak C—H⋯O inter­action generates inversion dimers. A Hirshfeld surface analysis shows that H⋯H contacts dominate the packing (86%) followed by O⋯H/H⋯O and C⋯H/H⋯C contacts, which contribute 3% and 10.4%, respectively.

Recently, I have made a series of blog posts about Redheffer matrices and the Mertens conjecture. After each of the posts, readers and colleagues offered suggestions to speed up the calculations. Here is a summary of what I have learned.... read more >>

"The Commission made binding commitments offered by T-Mobile CZ, CETIN and O2 CZ that will keep the benefits of network sharing whilst removing technical and financial disincentives to unilateral deployments and limiting information exchange, all to the benefit of Czech mobile user," Commission Vice-President Margrethe Vestager said in a statement.

; Credit: LA Johnson/NPR

Writing a graduation speech is a tricky task. Should you be funny, or sincere? Tell a story — or offer advice? For Yusef Pierce, a graduating senior in California, the job of putting together his public address was a bit more challenging.

"Being inside, I can't really refer to other graduation speeches," Pierce says. He's speaking by phone from inside the California Rehabilitation Center, a medium-security prison in Norco. "I was just trying to come up with what sounded like a graduation speech."

He is the first person to graduate with a bachelor's degree from the Inside-Out program at Pitzer College, a liberal arts school outside Los Angeles. In a normal year, the school would bring traditional students by bus to the prison to take classes alongside the students who are in prison.

Because of the coronavirus pandemic, those classes are happening online. Pierce shared his Zoom square with 10 other guys, all wearing the CRC's blue uniforms and seated at those classic classroom desks, where the chair and the table are attached. This spring, his classes included topics like feminism for men, microeconomics and mass incarceration.

In one of those classes on a recent evening this spring, professor Nigel Boyle goes around asking each student what they're looking forward to doing that week. Pierce replies: "I'm looking forward to doing a lot of homework!"

"Every professor wants a Yusef in your class," says Boyle, who leads the Inside-Out program and teaches Pierce's Wednesday night class about mass incarceration. "You want that student who's bright, does the work, but is also helping to bring along the others."

It was only natural then that Pierce would be one of the college's graduation speakers.

"We don't label the student speaker as a valedictorian," explains Boyle. "But it happens that Yusef has a 4.0, and he's got a really interesting story to tell."

Pierce is in his early 30s and is a bit of a nerd and a class leader. He also writes poetry and paints. "It is true that oppression often requires that individuals make themselves extraordinary in order to simply survive," reads his artist's statement in an online exhibit of his work. "My paintings are entire conversations on canvas."

Eventually, he says, he wants to be a college professor, working with formerly incarcerated students.

"So he wants my job," says Boyle, laughing, "and he'd be much better at it than I am."

Boyle serves as the academic adviser to all of the incarcerated students, and he has become a mentor to Pierce, navigating him through the graduation process. In one of the last classes of the semester, Boyle hosts an impromptu fashion show, wearing his own blue cap and gown, backing away from the camera to give the onlooking students a full view of his outfit.

The guys inside cheer and whistle. "Do a spin," one guy shouts. "Beautiful! Beautiful!" another yells.

As the cheering dies down, Boyle looks for Pierce on the screen. "He doesn't know this, so it may be a slight surprise," he tells the class, "but, Yusef, you will also be receiving these cords." He drapes dark orange cords around his shoulders. "These cords are for students who graduate with honors in their degrees. Congratulations, Yusef, you are going to graduate with honors."

***

The story of how Yusef Pierce wound up in these college classes, wound up inside prison at all, starts with trauma. When he was a teen, his older brother was shot and killed. "He was murdered in the front yard of our home, right in front of my face," he explains, "and so I had to call my mom and let her know what had happened." All these years later, it's still something he doesn't like to talk about. He considered putting it in his graduation speech, but took it out, worried it might be too much for his mom to hear.

"It had a traumatic effect on all of us," Drochelle Pierce tells me over the phone, from her house in Victorville, Calif. She remembers a change in Yusef around that time.

"It was just kind of one thing after another. He got into a little bit of trouble. He allowed people that he associated with to kind of influence him in a direction that really wasn't him." Yusef finished high school, but in his early 20s he was arrested and convicted of armed robbery. Drochelle Pierce says she was beside herself when she learned his sentence would be nearly 20 years. "I tell you, honestly, I never envisioned that Yusef would ever go to prison. Never, never. Never."

A few months into Yusef's prison sentence, she wrote him a letter. "What's done is done," she wrote. "You, now more than ever, must diligently seek and obtain higher education."

It wasn't a new message. Education had always been at the center of her relationship with Yusef. When he was young, he remembers riding in the car with his mom, a sociology textbook open on his lap. "She wouldn't let me turn on the radio," he says. "She would make me read to her."

"Oh, I made [my kids] read everything," Drochelle Pierce says. "If they read it out loud, I knew they were reading it. That's the only way I would know that they were actually reading anything."

Today, the two talk on the phone nearly every day. "He was always a deep thinker," says Pierce. She knows she sounds like a typical proud mother, but she can't help it: "Yusef is very smart."

In California, college classes can shorten a prison sentence. So when the opportunity first arose for Yusef Pierce to take courses in prison, it felt like simply a means to an end. "I just want to get home sooner," he remembers joking with a friend at the time. "If they gave us time off for going to college, I would walk out of here with a Ph.D.!"

But by the time Pitzer College started offering classes for a bachelor's degree, Pierce found to his surprise that he really liked college.

"I loved it because it gave me validation," he says. "To know that somebody was reading my stuff and that somebody felt like the things that I was thinking about and writing were worth something. I got really addicted to that validation, and it just really turned me into an overachiever. And I just took class after class after class."

That drive paid off.

After writing and rewriting a number of drafts, on May 15 Pierce delivered his final graduation speech to hundreds of Pitzer graduates and their family members and friends. The content he landed on? That letter his mom sent him all those years ago.

"I realize now that I've saved this letter because it was meant for me way back then to share it with you all today," he says, dressed in his white cap and gown, draped in a kente stole, with the prison classroom where he has spent so much time in the background. "It reads, 'Dear son, I was so glad to see you Monday ...' "

As he reads the letter aloud, he gets to the part where his mother, a big poetry fan, included the lines from Invictus, a poem by William Ernest Henley. Pierce looks directly into the camera as he reads; he knows this part by heart.

Out of the night that covers me,
Black as the Pit from pole to pole,
I thank whatever gods may be
For my unconquerable soul.

In the fell clutch of circumstance
I have not winced nor cried aloud.
Under the bludgeonings of chance
My head is bloody, but unbowed.

Beyond this place of wrath and tears
Looms but the Horror of the shade,
And yet the menace of the years
Finds, and shall find, me unafraid.

It matters not how strait the gate,
How charged with punishments the scroll,
I am the master of my fate:
I am the captain of my soul.

Drochelle Pierce watched the speech on her laptop at home, with family gathered around. "We were all crying. We were just boohooing. It was just so sweet," she says.

The final line of the poem:

It matters not how strait the gate, / How charged with punishments the scroll, / I am the master of my fate: / I am the captain of my soul.

"I love that so much," she says. "I sent that to my son because I wanted him to think in terms of 'OK, here you are now. What happens to you from this point going forward, it really depends on you.' "

She is proud of her son and inspired by him too. "Look what he did. He turned a bad situation into something very, very positive. Here he is, graduating with his degree."

This content is from Southern California Public Radio. View the original story at SCPR.org.

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